At the notoriously tricky Estadio Hernando Siles, first-half goals from Lucas Paqueta, Richarlison and Bruno Guimaraes proved the difference.
With the likes of Neymar, Casemiro, Vinicius Junior and Fred all rested, Tite's side was by no means dominant, but characteristically did enough to secure a 14th win out of 17 games.
Though qualification is not technically finished for Brazil, with its abandoned game with Argentina set to be rescheduled, that fixture with its arch rival will likely be nothing more than a glorified friendly for both teams as they prepare for the finals in Qatar.
The best chance in the opening 20 minutes fell to the host, with Henry Vaca cutting inside on Marquinhos and shooting straight at Allisson.
Bolivia was made to pay only moments later via fantastic individual work from Paqueta in the 24th minute, the Lyon man playing a one-two with Guimaraes before coolly converting with only Ruben Cordano to beat in the Bolivian goal.
With a simple tap-in, Richarlison doubled the advantage just before half-time. Fabinho drove up the pitch upon Brazil gaining possession and Antony picked out the Everton attacker free at the back post to provide the assist.
It wasn't all clear skies for the Selecao in the altitude of La Paz, with Alisson again called into action in the 52nd minute to keep out Ramiro Vaca's deflected effort.
Alisson was left scrambling only two minutes later with Henry Vaca providing a dangerous cross to the back post for his namesake, who could not get a foot onto the ball for what would have been a certain goal.
Brazil was ruthless when presented opportunities and Guimaraes spectacularly made it three in the 66th minute after another quick counter, volleying home a first-time volley after good work from Gabriel Martinelli.
Richarlison rounded off the scoring from a quick throw-in during injury time, following up Rodrygo's initial attempt after a Guimaraes dart behind the defensive line.