Born and raised in Jabaquara, a district of São Paulo, César Sampaio was spotted by Lima and invited to join the youth sides of Santos in 1983.

In January 1999, after being close to a move to Vasco da Gama, he returned to Palmeiras,[3] being team captain during the club's 1999 Copa Libertadores title.

[9] At the 1998 FIFA World Cup finals, he became remembered for scoring the first goal of the entire tournament in the 4th minute of Brazil's opening match against Scotland, a header from a corner by Bebeto on the left.

[11] Sampaio is also remembered for helping Ronaldo when he suffered a convulsive fit in the night before the 1998 FIFA World Cup final.

On 22 December 2019, César Sampaio left Comercial to join Tite's staff at the Brazil national team, as his assistant.