Cavani was part of the Napoli side that lost to Chelsea in the last 16 of the competition in 2012 after taking a 3-1 first-leg lead.
"To me I will be using the game looking for revenge, because I faced Chelsea with Napoli," FourFourTwo quotes him as saying.
"We didn't deserve to lose, although we didn't play well in London to get through but we showed a lot in Naples, where we were better than them.
"It's like revenge against one of the biggest teams in the world, with the best players and against a team who are playing in a really attractive league. It's awesome (the Premier League)."
Chelsea won 3-0 when the sides last met at Parc des Princes in the Champions League in 2004.