Carlo Ancelotti and Gareth Bale will get their first taste of a Spanish derby when Real Madrid welcome Atletico to the Bernabeu on Saturday.
The pair will be thrust into the spotlight for the fixture, with Italian coach Ancelotti - who arrived at the club from Paris Saint-Germain in the close-season - set to hand Bale his long-awaited home debut following his world record switch from Tottenham.
The winger has shaken off the thigh injury that forced him out of the warm-up ahead of Real's victory over Getafe last weekend and should take his place in the squad.
A 4-1 win in that game extended Real's undefeated start to the new season, with Ancelotti's side having dropped just two points in a 2-2 draw with Villarreal.
They were, though, made to work hard for their win away to Elche on Wednesday, which came in dramatic circumstances.
Cristiano Ronaldo's opener was cancelled out by Richmond Boakye in the 91st minute at the Estadio Manuel Martinez Valero.
But there was still time for more drama as Pepe was adjudged to have been fouled by Carlos Sanchez in the area, with Ronaldo duly converting from 12 yards in the sixth minute of injury time.
Atletico's early-season form has been even more impressive than that of their arch-rivals, with Diego Simeone's side having won all six of their league games so far, as well as picking up an opening UEFA Champions League victory over Zenit St Petersburg.
That run has been in no small part down to the goals of striker Diego Costa, who has already notched seven times in La Liga this season.
The Brazilian was linked with a move to Premier League outfit Liverpool in the close-season, but his decision to stay in the Spanish capital has thus far paid dividends.
Elsewhere, leaders and reigning champions Barcelona will look to extend their 100 per cent winning start to the season when they travel to the Estadio de los Juegos Mediterraneos to face winless Almeria.
New coach Gerardo Martino has enjoyed a fantastic start to his reign with the Catalan club, and their latest triumph came in a potentially tricky encounter at home to Real Sociedad, as they romped to a 4-1 home win.
Barcelona have already scored 22 league goals this season, and they will be confident of extending that record against an Almeria side that has shipped 15 goals in the league, with only Rayo Vallecano conceding more.
In other matches on Saturday, Vallecano travel to the Mestalla to play a Valencia side looking for a third straight league victory, while Real Sociedad play host to Sevilla, who earned their first league win of the term with a 4-1 drubbing of Vallecano on Wednesday.
On Sunday, Villarreal will bid to extend their bright start to the new campaign when they visit the Estadio Benito Villamarin for their clash with with Real Betis.
Having won promotion back to the Spanish top flight last season, Marcelino Toral's side have won three and drawn two of their five La Liga fixtures and occupy fourth spot.
Meanwhile, early-season strugglers Osasuna have the chance to kick-start their campaign when they welcome Levante to the Estadio El Sadar.
Osasuna have lost five times in the league so far, with their only success coming in a 2-1 triumph over Elche on September 20.
Sunday's other fixtures see Celta Vigo and Espanyol welcome Elche and Getafe respectively.
On Friday, Real Valladolid face Malaga, while Athletic Bilbao's trip to Granada ends the round on Monday.
|22||Á. di María|
|Coach: C. Ancelotti|
for Á. di María 46'
for Illarramendi 46'
for Isco 73'
|Chelsea turned Valencia´s head - Allardyce|
|Poyet spat was not a good look - Bruce|
|Gold ´hopeful´ over Reid deal|
|´No problem´ with Bruce, says Poyet|
|Sherwood confident in Villa upturn after derby win|
|Pulis stands by Foster after costly error|
|Boulogne 1 Saint-Etienne 1 (aet, 3-4 on penalties): Minnows´ run ends on penalties|
|Schalke want to buy Nastasic|
|Pardew feeling hard done by after Southampton defeat|
|Football League Review: Boro go top as Derby falter again|
|Koeman pleased with ´crucial´ victory|
|Agbonlahor eyes turnaround as Villa end wait for win|
|Equaliser at Hull hit my arm - Rodwell|
|Reus injury ´only a dead leg´|
|Lyon hope for long Lacazette stay|
|DFB-Pokal Review: Leverkusen shake off old foes Kaiserslautern|
|Aston Villa 2 West Brom 1: Benteke on the spot as Villa win at last|
|Hull City 1 Sunderland 1: Rodwell earns visitors a draw in dramatic encounter|
|Southampton 1 Crystal Palace 0: Mane wins it late on|
|Dynamo Dresden 0 Borussia Dortmund 2: Reus withdrawal overshadows Pokal progression|
|Bruce and Poyet clash in ugly touchline spat|
|Dortmund star Reus in new injury scare|
|Lyon success a source of pride for Gonalons|
|Juventus v Fiorentina: Allegri seeking improvement|
|Edu hails ´phenomenon´ Sanchez|
|´Huge money´ needed to take Cech away - Mourinho|
|Lazio v Napoli: Benitez calls for unity in trophy quest|
|West Ham´s Cole landed with FA charge|
|Leeds fan group want meeting with Hollywood star Crowe|
|Suso prepared to wait for Milan chance|
|Ashley fined £7,500 for influence in Rangers|
|Blanc praises Luiz´s versatility|
|Pochettino: League Cup heartbreak will help Spurs grow|
|Carver understands frustration with Van Gaal|
|AFC Champions League Review: Jeonbuk and Kashiwa win convincingly|
|Guardiola committed to Bayern amid City rumours|
|Hughes: Bruce is defending the indefensible|
|Espanyol v Athletic Bilbao: Stuani eyeing ´momentous´ cup final|
|Everton waiting on Baines fitness|
|I am not under pressure, Pellegrini insists|
|Guardiola demands focus ahead of Braunschweig clash|
|Van Gaal: Di Maria needs a year to settle|
|Luis Enrique vows to attack Villarreal|
|Jedinak hit with four-game ban|
|Mourinho guarantees Terry deal|
|Mowbray lands Coventry job|
|Strootman on schedule for Roma return|
|Mikel out for a month after surgery|
|Palace midfielder Jedinak accepts FA charge|
|Wigan chairman Whelan stands down, hands reins to 23-year-old grandson|
|Jedinak stays quiet on FA charge|
|England winger Johnson released on bail|
|Gareca signs four-year Peru deal|
|Sandro set for QPR return|
|Hull dealt Brady blow|
|Garcia going nowhere, insists Pallotta|
|Allardyce: Chelsea aren´t allowed to be off form|
|Arsenal boosted by Ramsey return|
|No early Barca return for Tello|
|Pirlo inspired stunning Tevez free-kick|
|Brunt vows to heap misery on Villa|
|Barry: Everton needs points on the board to avoid relegation scrap|
|Janmaat hails ´fantastic´ Van Gaal|
|Cahill vows to silence critics|
|Spurs legend Mackay passes away|
|Adrian: I get good results against Mourinho|
|Hoffenheim boss wary of rising expectations|
|Sturridge edging closer to his best - Rodgers|
|Kroos happy with deeper role|
|Terry ´fighting´ for Chelsea contract|
|Townsend: No excuses for Tottenham|
|Garcia applauds Roma´s ´magnificent´ comeback|
|Belenenses 0 Pacos de Ferreira 1: Moreira seals rare away win|
|Juve angry at Roma draw - Allegri|
|Roma 1 Juventus 1: Keita keeps slim Scudetto hopes alive|
|Celta Vigo 1 Elche 1: Controversial late penalty gives visitors a point|
|Turkish Super Lig Review: Gala extend lead at the top|
|Paris Saint-Germain v Monaco: Jardim rejects de-facto final talk|
|Stuttgart, Freiburg named in doping claims|
|Dyche hails Ings determination ahead of Liverpool showdown|
|Newcastle United v Manchester United: Mata out to make more memories|
|England winger Johnson suspended after arrest on underage sex charge|
|Liverpool back in the black|
|Jedinak charged with violent conduct|
|BREAKING NEWS: Police make arrest on underage sex charge amid reports England international is held|
|Schone delighted to extend Ajax deal|
|Montolivo and De Jong suffer injuries|
|Bayern Munich v Eintracht Braunschweig: ´Self-critical´ holders in no mood to ease off, says Muller|
|Tottenham v Swansea City: Pochettino out to banish League Cup disappointment|
|QPR v Arsenal: Austin ready for survival fight|
|Sherwood: No hard feelings over missing out on West Brom job|
|Chelsea and Everton fined for fracas|
|Villarreal v Barcelona: Final in sight for visitors|
|Stoke City v Everton: Howard calls for back-to-basics approach|
|Pearson: I understand Pellegrini pressures|
|West Brom sweating on fitness of Berahino and Ideye|
|Manchester City v Leicester City: Pellegrini demands response|
|Feyenoord and Roma face UEFA charges|
|Liverpool v Burnley: Rodgers full of respect for visitors|
|Brown has red card overturned|
|Rodgers heaps praise on Allen|
|Koeman critical of Jedinak elbow|
|Bruce hits back at Hughes over Figueroa challenge|
|Koeman sets 61-point target for Southampton|
|Ibe set to miss a month with knee injury|
|Klopp looking to maintain momentum|
|Bent out for three to four weeks with hamstring injury|
|Schmidt ready for Kaiserslautern clash|
|West Ham v Chelsea: Mourinho turning attention back to the league|
|Barca must not be distracted by Clasico, says Busquets|
|Terry rules out England return|
|De Boer demands more despite PSV win|
|Bony: We have to win every game|
|Subotic rejects Serbia call-up|
|Benitez frustrated at refereeing decisions|
|Real Madrid must learn from Villarreal draw - Marcelo|
|QPR announce losses of £9.8m|
|Rutten to leave Feyenoord|
|First trophy for ´new´ Chelsea - Mourinho|
|Icardi the future of Inter, says Ausilio|
|Patience needed from ´brilliant´ United fans - Rooney|
|Allen hails ´next level´ Coutinho|
|Points over milestones for Cisse|
|Hecking ´furious´ with Wolfsburg defence|
|CONCACAF Champions League Preview: DC United face uphill task to reach semis|
|AFC Champions League Preview: Al Ain enhanced, Wanderers prepare for Evergrande reunion|
|Coupe de France Preview: PSG, Monaco to meet again|
|Crouch happy to silence doubters|
|Blanc questions rivals´ mental strength as PSG gain ground|
|Kane: Fortune favoured Chelsea|
|Ancelotti defends Isco substitution|
|Rooney: Di Maria will come good|
|Stubborn Villarreal impress Real´s Pepe|
|PSG could not ´kill off´ Monaco - Van der Wiel|
|Serie A Review: Napoli suffer defeat at Torino, Lazio lurking|