David Villa opened the scoring from long range after 24 minutes and Andres Iniesta added a second 13 minutes later with Marco Estrada sent-off for a foul in the build-up to the goal.
But Rodrigo Millar scored two minutes after the break and, with Switzerland drawing 0-0 with Honduras, Chile progress to a last 16-encounter with Brazil while the European champions will face neighbours Portugal in the second round on Monday evening.
Villa scored from nearly 45 yards after Chile keeper Claudio Bravo needlessly came racing off his line to deal with a long ball and he saw Barcelona's new signing slide the follow-up into the empty net from near the left touchline.
Fit-again midfielder Iniesta then doubled the lead with a calm side-foot into the bottom corner with Villa this time the provider as he pulled the ball back to his new Camp Nou colleague who opened up his body and dispatched the ball past Bravo.
Estrada received a second yellow card for a tangle of legs with Fernando Torres in the build-up to the goal and it looked harsh as Estrada was not even looking at the Liverpool striker at the time.
Referee Marco Rodriguez of Mexico appeared to get that one wrong but Estrada was lucky still to be on the pitch after a tackle from behind on Iniesta after his first caution while Waldo Ponce should also have received a second yellow after treading on the ankle of Xabi Alonso just before the break.
Chile's lack of discipline undermined a bright start and Mark Gonzalez should have given the South Americans the lead following a cross from Jean Beausejour but he lost his footing and shinned his effort wide from close range.
Iker Casillas was also forced to claw an audacious chip from Alexis Sanchez behind for a corner while Gerard Pique did superbly to get a foot in just as Beausejour was about to pull the trigger - moments after the defender had spurned a great chance to make it 2-0 when heading over from close range.
Chile coach Marcelo Bielsa made a double change at half-time and it paid immediate dividends as Millar scored within 120 seconds of entering the action.
His 20-yard chip took a wicked deflection off Pique and looped over Casillas into the net.
At that point Switzerland needed to score twice to deny Chile a place in the next round and the message seemed to transmit to the players as the sting went out of the game.
Spain replaced Torres - who missed two good early chances - with Cesc Fabregas, and he tried to up the tempo while only a superb last-ditch tackle by Waldo Ponce denied Villa a certain goal.
But the last 20 minutes almost resembled a testimonial with Spain delighted to top the group after their surprise 1-0 defeat against Switzerland, while for the first time in history South America will have five teams in the last 16.
However Chile will face Brazil without key defenders Gary Medel and Ponce, plus midfielder Estrada, who are all suspended.
Match Facts
Chile v Spain
Goals 1-2
1st Half Goals 0-2
Shots on Target 2-2
Shots off Target 3-4
Blocked Shots 3-2
Corners 3-4
Fouls 21-13
Offsides 3-1
Yellow Cards 2-0
Red Cards 1-0
Passing Success 71%-86.5%
Tackles 26-19
Tackles Success 88.5%-63.2%
Possession 30.9%-69.1%
Territorial Advantage 50.4%-49.6%
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