Julio Cesar saved two spot kicks while William and Hulk couldn't find the target.
Mauricio Pinilla and Alexis Sanchez had penalties saved, before Gonzalo Jara missed the crucial final kick.
During the game itself, David Luiz gave Brazil the lead when he bundled in after Thiago Silva had flicked on Neymar's corner.
Chile equalised when Eduardo Vargas pounced on a defensive error and fed Alexis Sanchez who poked in.
Brazil's Hulk also had a goal disallowed in the second half when English assistant referee Michael Mullarkey judged the striker to have handled Marcelo's pass.
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