Hoffenheim striker Firmino latched on to Danilo's pass and took the ball around Chile goalkeeper Claudio Bravo.
It was the highlight of a low-quality match punctuated by fouls.
Chile's Gary Medel was lucky to escape unpunished for treading on Barcelona striker Neymar in the first half.
With the Copa America starting in Chile on 11 June, it was the last chance for the players to impress before the squads are announced on 1 June but enthusiasm appeared to be lacking.
Neymar's free-kick from deep was close to sneaking in at the far post and Bravo was forced to push the ball wide for a corner before Douglas Costa missed Brazil's best chance of the half.
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