The Barcelona star scored twice as the host nation condemned the Africans to their seventh straight World Cup defeat.
Neymar was at his best as Brazil earned a 4-1 FIFA World Cup win over Cameroon to finish top of Group A.
The idolized forward feasted upon a vulnerable defense with glee in Brasilia on Monday, his first-half double sandwiching Joel Matip's unlikely leveler.
Brazil ultimately progressed with a degree of comfort, the much-maligned Fred and substitute Fernandinho adding further goals after the interval to secure a last-16 tie against fellow South American side Chile.
Mexico was victorious against Croatia in Group A's other closing fixture, but failed to make up a goal-difference deficit as the home side retained top spot.
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While a routine triumph in which Brazil's star took his tournament tally to four goals will provide comfort, Luiz Felipe Scolari is unlikely to partake in too much back slapping.
Indeed, after coming through a group featuring no other major footballing powerhouse, Scolari is likely to demand more of his side as it prepares to face a Chile outfit that has impressed in the tournament to date.
The game immediately took on a frenetic nature as Paulinho and Vincent Aboubakar had goal-bound efforts blocked at either end.
It was Cameroon's susceptible back line that was first to be breached when Neymar, inexplicably unmarked, cleverly turned home Luiz Gustavo's low cross from the left.
Brazil's golden boy came agonizingly close to a second soon after, Charles Itandje producing a fine save to keep out his fizzing volley.
Despite the defense appearing increasingly hapless, Cameroon looked dangerous at the other end and fired a warning shot as Matip's header rattled the crossbar.
Not heeding the lesson proved costly for the home team, too, as Matip side-footed Allan Nyom's cross into an empty net the next time he got an opportunity.
With Brazil seeking a response to increasing Cameroon pressure, Neymar again stepped up, albeit with the help of some more schoolboy defending. Afforded far too much space once more, the Barcelona forward cut inside from the left and sent Itandje the wrong way.
While those in front of him wilted in the face of pressure, Itandje was at least attempting to provide a steadying influence, getting down quickly to turn away Hulk's speculative hit.
The goalkeeper had to be on high alert again after the interval, denying Hulk and Neymar in quick succession.
But he could do little as another Brazilian, this time Fred, was left free in the area, the under-pressure forward heading home David Luiz's pass.
Brazil opted for a more controlled approach thereafter, epitomized by the team's willingness to withdraw Neymar after 71 minutes.
Even then, the drama was not finished, with Mexico threatening to steal the group after scoring three quick goals against Croatia.
However, the impressive Fernandinho, who came on as a halftime replacement for Paulinho, settled any nerves with a cool finish following a fine move involving Oscar and Fred.