Defending champions Spain have fallen at the first hurdle as a 2-0 defeat to Chile means they have no hope of progressing to the knockout stages of the World Cup.
Vicente del Bosque had led Spain to glory at the 2010 World Cup and Euro 2012 but, following his side's 5-1 humbling against Netherlands on Friday, a reaction was required to avert a group-stage exit.
They had produced such a reaction four years ago when bouncing back from a defeat in their opener to Switzerland, but appeared for the most part to be a pale imitation of their 2010 vintage.
On 20 minutes, Chile broke the deadlock, carving the Spain defence open as Arturo Vidal, Alexis Sanchez and Charles Aranguiz combined before setting up Eduardo Vargas to skip around Iker Casillas and finish.
Just before half-time, Spain's fate worsened as Casillas failed to deal with a Sanchez free kick, allowing Aranguiz to poke home a second.
Spain injected more urgency into their game at the start of the second half, and Sergio Busquets spurned a golden opportunity to bring his side back into the game, but they could never exercise the kind of control that had been the hallmark of their success in recent years and were unable to force a goal.
Spain and Australia have both failed to register a point from their opening two fixtures and have no chance of progressing to the round of 16. Chile and Netherlands will meet in Sao Paulo on Monday to determine who will advance as winners of Group B.
Spain suffered the humiliation of being the first reigning champions to be knocked out of the World Cup after just two matches as Chile sent their tens of thousands of fans in the Maracana into rapture.
A tactical masterpiece from Chile's Argentine coach Jorge Sampaoli laid the foundation for the South Americans to humble their more-glamorous European opponents.
It is not the first time the reigning world champions have failed to make the knockout rounds - among others, Italy suffered that indignity in 2010 and so did France in 2002 - but never before has it happened after the first two games.
The 5-1 hiding handed out by Netherlands in the opening match was still reverberating for Spain, and the pattern of that nightmare second half of last Friday night continued in the same agonising vein.
Del Bosque's side appeared frozen into inaction, and it did not help that they were playing a Chile side whose spirit was stoked by tens of thousands of fans bouncing off the walls of the Maracana - in some cases literally as thousands without tickets remained outside the stadiums with around 200 bursting through a security cordon prior to kick-off.
From the start, Chile - who have looked hugely impressive in the last couple of years - were fired up for this fray. They served notice of their threat when Gonzalo Jara headed over from a good position.
Spain knew they had to win and Claudio Bravo in the Chile goal stood in Xabi Alonso's way when the Real Madrid midfielder pounced on Andres Iniesta's deflected pass with only the keeper to beat.
He looked certain to score but Bravo stopped it with one hand at close range, and Alonso's next involvement was to lose the ball in the move which saw Chile go ahead.
Sanchez snapped up possession and played in Aranguiz, who picked out Vargas with a brilliant centre. The Valencia forward kept his head while Spain were losing theirs and neatly sidestepped Casillas before sliding it home.
Alonso attempted to make amends but blasted high and wide from Diego Costa's lay-off, before the striker scuffed a shot into the turf and side-netting as Spain's frustrations increased.
Two minutes before half-time and Spain's looming crisis became a fully-fledged disaster.
Casillas, heavily criticised after the Netherlands debacle, did himself no favours with a poor double-handed fist at Sanchez's gentle free kick and the ball dropped to Aranguiz, who controlled it and then toe-poked back past the sorry keeper to make it 2-0.
Another bad miss from Costa, who was mercilessly taunted by the Chile fans, was followed by Jordi Alba spraying his shot wide as desperation set in for Spain in the second half.
Chile then turned rather wasteful, failing to kill off the game completely with Vargas shooting straight at Casillas, Mauricio Isla scooping over at full-stretch and Sanchez dallying too long when in space.
Del Bosque sent on Fernando Torres and Santi Cazorla to try a last-ditch rescue attempt and the Arsenal midfielder came close to scoring, denied by a sprawling save low to his right by Bravo with 10 minutes left.
Bravo was bravura to the last with more top-class saves, notably from Cazorla's free kick.
Spain looked like broken men. After the 2010 triumph sandwiched by two European Championship wins, their world has come crashing down.