Both sides had chances in an end-to-end second period, but neither could find a winner as the match headed for extra-time.
It was a similiar story in extra-time, with chances few and far between as the match headed for penalties.
Brazil came through the shootout, however, with Neymar scoring what was the winning penalty in a 3-2 success.
Read how it all unfolded in Sports Mole's minute-by-minute live commentary of the action below.
BRAZIL: Cesar; Alves, Luiz, Silva, Marcelo; Fernandinho, Gustavo; Hulk, Oscar, Neymar; Fred
CHILE: Bravo; Silva, Medel, Jara; Isla, Aranguiz, Diaz, Mena; Vidal; Sanchez, Vargas
Brazil vs Chile - who do you fancy people?? I'm going for a Neymar inspired win for Brazil....they have to contain Vargas & Sanchez though!— Rio Ferdinand (@rioferdy5) June 28, 2014