Laurent Blanc's men face Jose Mourinho's side in the first leg of their quarter-final tie in the French capital on Wednesday, with the return trip coming six days later.
Desailly does not think that PSG have any chance of winning in west London, suggesting that Zlatan Ibrahimovic and Co. will go for the jugular in the opening game to make up for what he foresees as inevitable defeat in the latter tie.
|4/1||Zlatan Ibrahimovic is 4/1 with William Hill to score two or more goals for Paris Saint-Germain when they host Chelsea|
"When you see the quantity and money they’ve spent, for the French league, it's amazing. The Champions League has the sweetness now; the French league doesn't attract them anymore. They've won it two times already, they really want the Champions League.
"It's going to be a tough game. All will be decided in Paris.
"If Chelsea manage to score or succeed in Paris, I don't see Paris coming back to Stamford Bridge. With the statistics Chelsea have at home, Paris can't win."
Mourinho's men head into the tie on the back of a shock 1-0 defeat to relegation-threatened Crystal Palace, which has put their title chase in jeopardy and allowed Liverpool to overtake them at the top of the Premier League.
In France, PSG edged a 1-0 win over Nice on Friday which helped them to extend their lead at the top of Ligue 1 to 13 points with just seven games left to go.