Brazil: David Luiz, Marcelo and Neymar scored, Willian and Hulk failed to score.
Chile: Aranguiz and Diaz scored, Pinilla, Sanchez and Jara failed to score.
The match went into the tie-breaker phase after it ended 1-1 at the end of the extra times.
Brazilian goalkeeper Julio Cesar, who was adjudged the man of the match, played a significant role during the shoot-out.
Brazil, who haven't lost a match on their home soil since 1975, gave away the early advantage during the penalty shoot-out as Chile failed to score from their first two scores. But Neymar, who scored his fifth goal of the tournament, converted a crucial penalty to put the onus back on Chile's Gonzalo Jara who hit the bar.
Brazil had more possession and created more chances but still couldn't penetrate the solid defence of Chile. As a result, the match score remained 1-1 at the end of the extra time.
Former Chelsea player David Luiz scored for Brazil in the 18th minute of the match but Chile drew level 14 minutes later when Alexis Sanchez scored his second goal of the tournament.
Brazil made one changes to their side by bringing in Ferdinandinho in place of Paulinho while Chile played the same XI that took the field against Spain.
The second half of the regulation team did not see any goal but was a tighter affair. Brazil could have taken a lead in this time when forward Hulk netted the ball but the referee turned it down after concluding that it was controlled with hand.
This was Brazil's fourth win over Chile in the World Cup finals. Brazil will meet the winners of Colombia and Uruguay in the quarter-finals.
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