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'
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