In a repeat of the Beijing 2008 showpiece, the South Americans once again got the better of their arch-rivals, seeing them off by the same 3-1 score that was good enough four years ago.
As a result, the USA's wait for Volleyball gold goes on - this was their 10th failed attempt.
The USA started the final as the in-form team, with front-row pairing Foluke Akinradewo and Destinee Hooker virtually unplayable in their games so far, one of which was a 3-1 win over Brazil in the group stages.
And they began tonight in that manner, threatening to overpower Brazil as they stormed to the opening set in just 21 minutes.
Somehow, though, Brazil used the end-of-set break to completely transform themselves, returning to the court to produce the most devastating spell of Volleyball any side has produced throughout the 37 games that had preceded this one.
Their attack became virtually unplayable owing to its speed, and with Hooker shut down and restricted to a tournament-low 14 points, they stormed to victory, proving coach Roberto Guimaraes was not wrong when he said he had learned the lessons of the round-robin defeat.
'This is a wonderful feeling,' said Brazil coach Jose Roberto Guimaraes afterwards.
'For me, the US were the favourites before this match. We played very well tactically.
'After the second set we really played wonderful. We were serving well and we didn't make mistakes on reception.'
Earlier, Japan took the bronze medal by securing a straight-sets success over Republic of Korea.
Masayoshi Manabe's side displayed a greater appetite from the first point as they wrapped up a first Games podium finish since 1984.