The Portuguese masterminded a 3-0 victory at Parc des Princes in the group stage of the UEFA 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 quarter-finals 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 look set to retain their Ligue 1 title, as they hold a seven-point lead over Monaco with seven games remaining, and come into the game on the back of a nine-match winning streak in all competitions.
Big-spending PSG have also lost just one of their last 38 home games in all competitions, and possess two of the most dangerous strikers in world football in Sweden captain Zlatan Ibrahimovic, who played under Mourinho at Inter, and Uruguay star Edinson Cavani.
Blanc guided the Parisian outfit to the quarter-finals of the competition last season, but agonisingly failed to secure a place in the last four as they lost on away goals to Barcelona.
They look 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 last 16.
While PSG are riding on the crest of a wave, Chelsea head into the tie on the back of a shock 1-0 Premier League defeat at Crystal Palace, which led to Mourinho writing off their domestic title hopes.
The former Real Madrid coach has maintained throughout the season that his side are a work in progress in his first campaign back in England, but they are only two points behind Premier League leaders Liverpool as well as still being in the hunt to win the Champions League.
The London club beat Galatasaray 2-0 in the second leg of their last 16 tie to progress 3-1 on aggregate, but facing the French champions will be a different proposition altogether.
Captain John Terry put Chelsea in front when they 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, criticised 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 be without Netherlands right-back Gregory van der Wiel (knee) and also has a concern over forward Jeremy Menez (illness).
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