Spain pressed in the second period, but could not find a goal as the holders were eliminated after just two matches.
Read how it all unfolded in Sports Mole's minute-by-minute live commentary of the action below.
SPAIN: Casillas; Azpilicueta, Martinez, Ramos, Alba; Busquets, Alonso, Iniesta; Pedro, Costa, Silva
CHILE: Bravo; Jara, Silva, Medel; Mena, Aranguiz, Diaz, Isla; Vidal; Vargas, Sanchez
13 - Only David Villa (16) has scored more goals than Pedro for #ESP since their title-winning 2010 World Cup. Shaker.— OptaJose (@OptaJose) June 18, 2014
Complete chaos in the Maracana press centre. Group of Chile fans running amok pic.twitter.com/2ngmjZqfWi— Gavin Hamilton (@WorldSoccerEd) June 18, 2014
It's a real mess here. Hopefully no one hurt. pic.twitter.com/8QJ4Shc3IA— Matthew Stanger (@MatthewStanger) June 18, 2014
Both teams are out warming up, Spain at the far end, and Chile nearest us pic.twitter.com/p4lGOcMKjw— Ian Abrahams (Moose) (@BroadcastMoose) June 18, 2014
Chile fans being led away by Brazilian security forces in long lines, hands on each other's backs. Now under control pic.twitter.com/gV86EcIGFk— David Ornstein (@bbcsport_david) June 18, 2014