PSG are currently top of Group F with seven points from their opening three fixtures, and Cavani believes that Laurent Blanc's side can carry their form into the knockout stages if they secure a spot in the next round.
"I think we can, and we could have last season," the Uruguayan told Le Parisien. "We just missed a bit of luck, even though I don't like this word.
"But this year, we're more experienced, we're better prepared and these are two necessary conditions to win the Champions League."
Cavani scored as PSG came from behind to beat Lorient in Ligue 1 on Saturday.