The home side heads into the Champions League clash having won its last nine games, while the Portuguese has ruled out Premier League title success after defeat to Crystal Palace.
The Portuguese masterminded a 3-0 victory at Parc des Princes in the group stage of the Champions League in September 2004, and the two clubs then played out a goalless draw at Stamford Bridge just over two months later.
However, the prospect of facing PSG in the quarterfinals of Europe's premier club competition will be much more daunting for Mourinho when the sides renew their rivalry a decade on in Paris this week.
Laurent Blanc's side looks set to retain the Ligue 1 title, as the club holds a 13-point lead over Monaco with seven games remaining, and comes into the game on the back of a nine-match winning streak in all competitions.
Big-spending PSG has also lost just one of its last 38 home games in all competitions and possess two of the most dangerous strikers in world football in Zlatan Ibrahimovic, who played under Mourinho at Inter, and Uruguay star Edinson Cavani.
Carlo Ancelotti guided the Parisian outfit to the quarterfinals of the competition last season, but agonizingly failed to secure a place in the last four as the club lost on away goals to Barcelona.
The team looks more than capable of making up for that disappointment this time around, though, as was evident in a 6-1 aggregate win over Bayer Leverkusen in the round of 16.
While PSG is riding on the crest of a wave, Chelsea heads into the tie on the back of a shock 1-0 Premier League defeat at Crystal Palace, which led to Mourinho writing off the club's domestic title hopes.
The former Real Madrid coach has maintained throughout the season that his side is a work in progress in his first campaign back in England, but the Blues are only two points behind Premier League leader Liverpool as well as still being in the hunt to win the Champions League.
Chelsea beat Galatasaray 2-0 in the second leg of their round-of-16 tie to progress 3-1 on aggregate, but facing the French champion will be a different proposition altogether.
Captain John Terry put Chelsea in front when the club won at PSG in 2004, but that must seem a distant memory as he attempts to banish the memory of a headed own-goal that proved costly at Palace at the weekend.
Mourinho, who is attempting to become the first manager to win the Champions League with three different clubs, criticized the mentality of some of his players after the Palace defeat and looks set to make changes.
Ramires has been serving a domestic suspension, but is set to return in Paris, although it remains to be seen if Ashley Cole (knee) will be back in the squad.
Striker Samuel Eto'o (hamstring) is doubtful once again, while Marco van Ginkel (knee) is definitely out.
Blanc, meanwhile, will very likely be without Netherlands right back Gregory van der Wiel (knee) and also has a concern over forward Jeremy Menez (illness).