Alexis Sanchez's brace proved the difference as an assured Chile handed England a 2-0 defeat, their first for a year at Wembley.
The Barcelona forward scored three times in his country's last two FIFA World Cup qualification games as they plotted a successful route to the finals in Brazil, and he stole in to net a seventh-minute header ahead of Leighton Baines, who was given the nod ahead of Ashley Cole at left-back for England.
Chile's slick interplay regularly caused problem's for England's defence, but visiting goalkeeper Claudio Bravo was forced into sharp stops from Frank Lampard and Jack Wilshere in an enjoyably open first-half.
The usual flurry of substitutions after the break disturbed the game's flow as England's failure to locate the final pass undermined their efforts and, in injury time, Gary Cahill carelessly gave away possession and Sanchez produced a superb chipped finish to put gloss on the victory.
In the first of three friendlies before selecting his final 23-man squad for the 2014 FIFA World Cup finals in Brazil, England manager Roy Hodgson handed debuts to Celtic goalkeeper Fraser Forster and in-form Southampton duo Adam Lallana and Jay Rodriguez.
Chile were without key man Arturo Vidal, who suffered a thigh strain in Juventus's 3-0 weekend win over Napoli.
England started brightly but after Phil Jones and James Milner tested an uncertain-looking Bravo, opposite number Forster’s first act was to pick the ball out of his net.
Jones' block thwarted Charles Aranguiz, only for Sanchez to dive across Baines and head home when Jean Beausejour sent the ball back into England's box from the left.
Forster beat away Beausejour’s 14th-minute effort as a busy night shaped up for both goalkeepers - Bravo athletically turning Lampard’s deflected free-kick over the crossbar before fisting Wilshere’s rasping left-footer away.
But England remained defensively unsettled by Chile’s pace and directness and, after Gary Medel wasted a free header, Beausejour offered an ill-fitting conclusion to a wonderful 31st-minute counter- by failing to get a shot off as Forster forced him wide.
Just as Chile’s passing game was starting to dominate, England produced their best move of the match in the 44th minute – Wilshere and Wayne Rooney combining to feed Lallana, whose shot was deflected past the far post.
Despite a flurry of corners early in the second period, England were chasing shadows once more as Chile weaved through their defensive efforts and Eugenio Mena's cross was fumbled by Forster.
The first contribution of substitutes Chris Smalling and Gonzalo Jara was to receive bookings for an altercation at an England corner with an hour played after Baines’ free-kick dropped wide via the wall.
By that time, regular substitutions had taken their toll on the contest but Sanchez was still on hand to provide a delightful finale.
He stole in deep into injury time as the visitors claimed an upset win.
|Coach: R. Hodgson|
for J. Rodriguez 57'
for P. Jones 57'
for J. Milner 66'
for F. Lampard 71'
for J. Wilshere 71'
for A. Lallana 77'
|Trophies still the focus for Guardiola|
|Mignolet wants ´fair´ Karius battle|
|Ancelotti impressed by motivated Bayern|
|West Ham ´unreservedly condemn´ crowd trouble|
|Allegri praises strike duo after win over Sampdoria|
|De Boer praises two-goal Icardi after vital win|
|Chelsea were ´unlucky´ with missed chances, insists Conte|
|Mourinho: I´ve never had fans like these|
|Nacho´s goal better than my Champions League final volley - Zidane|
|Borussia Dortmund 1 Union Berlin 1 (aet, 3-0 pens): Weidenfeller shootout heroics seal progress|
|Bilic: Crowd trouble distracts from great West Ham win|
|Kompany told me he couldn´t play anymore - Guardiola|
|Liverpool and Manchester United handed home quarter-finals|
|Inter 2 Torino 1: Icardi double alleviates pressure on De Boer|
|Manchester United 1 Manchester City 0: Mata extends Guardiola´s winless run|
|West Ham 2 Chelsea 1: Crowd trouble tarnishes Hammers´ route to quarter-finals|
|Cultural Leonesa 1 Real Madrid 7: Morata and Asensio star in BBC´s absence|
|Bayern Munich 3 Augsburg 1: Green´s first goal sends holders through|
|Juventus 4 Sampdoria 1: Rapid start sets champions on their way|
|Crafty Suarez is world´s best striker - Godin|
|Mancini: Balotelli has wasted years but can bounce back|
|Rami rejected ´risky´ PSG move|
|Neymar would have cost PSG €430m, claims father|
|Sacchi warns Bayern players over Ancelotti temper|
|Valencia ´pleased´ with RFEF bottle ruling|
|Mourinho apologises to Utd fans for Chelsea thrashing|
|Barcelona lash out at ´totally reprehensible´ RFEF comments|
|Jacob leaves Marseille amid rumours of Zubizarreta appointment|
|Lavezzi added to Argentina squad as Dybala drops out|
|Del Bosque: Mourinho had a point on Conte|
|N´Zonzi in talks over Sevilla extension|
|Allardyce successor ´will not be a mercenary´ - Glenn|
|Aubameyang like a rocket, Lewandowski perfect - Riedle|
|RFEF fines Valencia, warns Barca over bottle incident|
|Wenger tells Iwobi to improve his finishing|
|Barcelona without Mathieu for three weeks|
|Kimmich draws inspiration from Xavi|
|Vazquez signs new Madrid deal|
|Higuain the best striker in the world - Nedved|
|Wolfsburg regret De Bruyne, Perisic sales|
|Parejo slams Neymar for ´inciting´ Valencia fans|
|Gundogan predicts ´very lively´ Manchester derby|
|Luis Enrique satisfied with Supercopa workout|
|Messi could join Newell´s after World Cup - Maxi Rodriguez|
|Ibrahimovic wants United to be the boss of City|
|Schmidt on the bus as Lotte book ticket for next round|
|Pogba still adapting to Premier League, says Mourinho|
|Southgate hails influence of demoted Rooney|
|Lille ready to heap more pressure on PSG as Corchia dreams big|
|I´m among top 20 LaLiga coaches, jokes Luis Enrique|
|Brattan earns Socceroos call-up|
|Pochettino pleased with Janssen|
|Klopp never questioned Sturridge quality|
|Barcelona downed by Espanyol in Supercopa|
|Heavy Milan defeat ´just a bump in the road´ - Montella|
|Pochettino wanted Liverpool debutant sent off|
|Klopp happy to entertain as Liverpool youngsters earn their spurs|
|Leverkusen dumped out by 10-man minnows|
|Wenger praises Oxlade-Chamberlain work ethic|
|Wenger praises Oxlade-Chamberlain work ethic|
|Tuchel unaffected by Real Madrid rumours|
|I would like to pick Toure, believe me - Guardiola|
|Genoa 3 AC Milan 0: Unbeaten run comes crashing to an end as Paletta sees red|
|Liverpool 2 Tottenham 1: Sturridge at the double to book quarter-final spot|
|Arsenal 2 Reading 0: Oxlade-Chamberlain brace secures safe passage|
|Football world mourns Carlos Alberto|
|81 per cent win ratio and more goals than Bayern Munich - Two years of Messi, Suarez and Neymar|
|Ridgewell reportedly arrested for drink driving|
|Verratti not leaving PSG - agent|
|Costa competition benefitting Batshuayi, says Conte|
|Pele hails ´friend and brother´ Carlos Alberto|
|Bailly confirms two-month lay-off|
|How Carlos Alberto established his legacy as one of the greats|
|Allegri hints at Marchisio return|
|Lewandowski has not renewed with Bayern - agent|
|Carlos Alberto: Capita´s World Cup triumph in numbers|
|Hull´s Snodgrass out for a month|
|Keita reveals Arsenal, Manchester City, Liverpool snub|
|Mikel not giving up on Chelsea career|
|Former Brazil captain Carlos Alberto dies|
|Guardiola wants to help ´special player´ Aguero|
|Roma welcome back Strootman, Rudiger for Sassuolo clash|
|Wolves confirm Zenga dismissal|
|Bruce lauds Rooney as a world ´great´|
|Raiola made €27m on Pogba move, reveals Juventus director|
|Dortmund injury woes worsen with Aubameyang|
|De Bruyne out of Manchester derby|
|Conte: I always show respect to opponents|
|FIFA fines RFEF over Madrid, Atletico breaches|
|Pedro backs Conte amid Mourinho spat|
|Big clubs would fight for Edwards if he was Brazilian - Pochettino|
|They boo Ronaldo, they booed me as well - Zidane|
|De Boer fed up of sacking talk|
|Neuer: Bayern have no room for error|
|Bilic praises Conte´s ´aggressive´ demeanour|
|Di Maria will bounce back - Motta|
|EFL opens investigation into Watford over ´forged´ bank letter|
|Hummels admits RB Leipzig a serious threat for Bayern|
|Pedro reveals Barcelona talks|
|De Bruyne: I have no problem with Mourinho|
|Casillas: I have not retired from Spain duty|
|Raul backs under-fire Ronaldo for Ballon d´Or glory|
|Mourinho and United must lower expectations - Xavi|
|Hands off! Milan CEO insists Donnarumma will stay|
|Glory coach Lowe accepts ban|
|Scolari extends contract with Guangzhou Evergrande|
|Guardiola eliminated City doubts - De Bruyne|
|Klopp lauds Ings for ´perfect´ response|
|Wenger: Perez needs to take chance|
|Boys to men: Mourinho challenges United players|
|Kompany committed to bargain with City medics|
|´Insipid´ Hazard overlooked for Ballon d´Or|