Paris Saint-Germain star Neymar scored a hat-trick in Brazil’s 4-2 win at the Estadio Nacional in Lima on Tuesday night.
The 28-year-old, who has scored 64 times in 103 appearances for his country, moved two ahead of Ronaldo and lies 13 goals behind record goalscorer Pele.
Richarlison got Brazil’s other goal while Andre Carrillo and Renato Tapia were on the scoresheet for the hosts.
Elsewhere, Joaquin Correa scored the decider 11 minutes from time as Argentina scraped past Bolivia 2-1 at the Estadio Hernando Siles in La Paz.
Moreno Martins gave the hosts the lead midway through the first-half before Lauro Martinez levelled on the stroke of half-time.
Lionel Messi and Martinez then combined to tee up Correa to thrash home the winner.
Giants lead the way
After two of the 18 qualifiers, Brazil sit top of the Conmebol table on goal difference. Argentina are second and Colombia are third with four points following their 2-2 draw in Chile on Tuesday night.
Ecuador picked up their first points of the campaign with a 4-2 romp past Uruguay in Quito.
They took the lead on 15 minutes as Moises Caicedo flicked home a header from an Angel Mena cross.
Michael Estrada doubled the advantage on the stroke of half-time and he smashed home his second from 20 metres just after the pause.
Ecuador's final goal was a work of art as Alan Franco's reverse pass bemused Uruguay's defence and Gonzalo Plata rolled his foot over the ball to commit both sliding defender Ronald Araujo and goalkeeper Martin Campana before stroking the ball into the far corner.
Luis Suarez scored his record-extending 61st and 62nd goals for Uruguay with a pair of late penalties that were no more than a consolation.
