Neymar has surpassed Pele as Brazil's male all-time top scorer with two goals in a 5-1 win over Bolivia.
The forward, 31, who went into the World Cup qualifying match tied with legend Pele on 77 goals, missed a penalty before scoring twice in the second half on his 125th appearance.
"I never imagined reaching this record. I'm no better than Pele or any other player for the national team," he said.
Marta has scored a record 122 goals in 189 matches for Brazil's women's team.
Pele, who died in December aged 82, scored 77 goals in 92 appearances between 1957 and 1971. He was widely regarded to be one of the greatest footballers to ever play the game.
His official account on social media platform X paid tribute to Neymar's achievement.
"Congratulations Neymar for surpassing the King in goals for Brazil. Surely Pele is applauding you today!" it said.
Brazil coach Fernando Diniz said: "He came to do what he did: have fun, score two goals and break the record."
Neymar became the world's most expensive player when he joined Paris St-Germain from Barcelona for £200m in 2017.
He left the French side in the summer to join Saudi Pro League team Al-Hilal.
"He is a very big idol, people must recognise him and accept him," Diniz added.
Elsewhere, Uruguay started their South American qualifying campaign with a 3-1 win against Chile under their new coach, former Leeds United boss Marcelo Bielsa.