The Barcelona forward scored the 100th goal of the tournament in Brazil's 100th World Cup finals match to put the hosts ahead in the 17th minute. He restored their lead before the interval after Joel Matip had equalised for Cameroon.
Fred got Brazil's third early in the second half with substitute Fernandinho adding a late fourth.
Brazil's win, combined with Mexico's 3-1 victory against Croatia in the other Group A game in Recife, ensured that they progress as group winners, ahead of Mexico on goal difference.
Cameroon were already out of the tournament after losing their opening two matches, but the Indomitable Lions had the advantage of playing without any pressure.
Volker Finke's men passed the ball confidently early on and Vincent Aboubakar gave the hosts something to think about with a shot that was blocked by Marcelo, but it was Brazil who took the lead.
The opening goal came as a huge release for Brazil and their fans in the crowd of over 69,000. Neymar's coolly sidefooted into the far corner of the net first-time from a low Luiz Gustavo cross.
It was the first time in the tournament that Scolari's side had scored the first goal of a game, and both Neymar and Fred came close to increasing their advantage, the latter lunging desperately to connect with a Paulinho cross but unable to scramble the ball home.
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