In the first leg of the preliminary round tie Ney Franco's Sao Paulo, who won the Copa Sudamericana last month, showed no mercy and took a seemingly unassailable lead ahead of the second leg next Wednesday.
Jadson was the man of the match with one goal and two assists, starting when he set up Osvaldo to open the scoring in the eighth minute with a neat finish into the top left corner.
Bolivar tried to respond and had a couple of sights of goal but in the 20th minute, Jadson and Aloisio combined to set up Luis Fabiano for the second goal.
In first-half injury-time Bolivar keeper Marcos Arguello failed to hold Aloisio's shot and Luis Fabiano made it 3-0.
Osvaldo added another for Sao Paulo 14 minutes after the interval and penalty-taking goalkeeper Rogerio Ceni rounded off the scoring from the spot four minutes later.
Ney Franco told reporters he was delighted with the form of Jadson, who relegated recently-signed star Ganso to the bench.
He said: "I cannot leave without talking about Jadson. You journalists are worried about Ganso, but I think Jadson was the best player tonight. His level is high enough to play for the national team."
The return leg will be played 3,800 metres above sea level in La Paz and Franco continued: "We made an important step but we have one match left. We have one week left to prepare our shape."
Also on Wednesday night, Ecuadorian giants Liga Deportiva Universitaria claimed a 1-0 win over Brazil's Gremio.
Carlos Feraud netted the winner with 15 minutes remaining in the game at the Estadio Casa Blanca, in Quito.