Barcelona superstar Neymar's 49th international goal in his 73rd appearance took him one clear of Zico on Brazil's all-time topscorer's list.
Still only 24, Neymar should reach Pele's all-time record of 77 goals from 91 games with something to spare if he continues to score at his present rate.
The Brazilian talisman was eventually substituted midway through the second half at the Estadio das Dunas in Natal, leaving the field to a loud ovation for his role in another impressive Brazilian win.
It was also a third consecutive victory from three games for new manager Tite, who was appointed after the sacking of Dunga in June.
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A sparkling first half performance effectively secured the points for Brazil, with Neymar, Philippe Coutinho, Filipe Luis and Gabriel Jesus all finding the net to put the hosts 4-0 up at half-time.
Coutinho's Liverpool team-mate Roberto Firmino made it 5-0 with a 75th-minute header.
Neymar fired Brazil into the lead on 10 minutes, working a wonderful one-two with Manchester City teenager Gabriel to slice open the Bolivian defence before tapping into an empty net.
Neymar then set up Brazil's third with a surging run that drew four Bolivian defenders before he threaded a pass through to Luis who drilled home his shot from just inside the penalty area.
Gabriel then put the seal on a mesmerising opening 45 minutes with Brazil's fourth goal.
Once again, Neymar was the architect, bursting clear as Brazil broke out of defence swiftly before picking out Gabriel who lifted a delicate chip above the on-rushing Bolivia goalkeeper Carlos Lampe.