Atletico Madrid v Chelsea: Predicted lineups
The Portuguese cut a frustrated figure as he witnessed his Blues side lose ground in the Premier League title race in a 2-1 setback to Sunderland on Saturday, a defeat that saw his 77-match unbeaten league run at Stamford Bridge come to an end.
Following that disappointment, Mourinho's post-match press conference had a somewhat sarcastic feel to it, as he offered congratulations to official Mike Dean - who had awarded Sunderland a controversial penalty that was converted by former Chelsea forward Fabio Borini - as well as Mike Riley, the general manager of the Professional Game Match Officials Board, which is responsible for appointing referees to Premier League matches.
Now, the 51-year-old must prepare his charges and focus on what is likely to be Chelsea's best chance of silverware this season.
But victory will not come easy in Tuesday's semi-final first-leg encounter at the Vicente Calderon, against an Atleti side that refuse to relinquish their grasp on top spot in La Liga.
Diego Simeone's men have won eight straight matches in the Spanish top flight in what has been a superb campaign and remain favourites to dethrone reigning champions Barcelona.
Perhaps more impressively was the way that Atleti ensured their first semi-final in Europe's premier competition since 1974, as they overcame Barca 2-1 on aggregate in the last eight.
The way in which Simeone's side quelled the threat of superstar Lionel Messi over the two legs was a particular highlight.
However, Chelsea have oft proved their mettle in the Champions League in recent seasons, including lifting the famous trophy in 2012 following a penalty shootout victory over current champions Bayern Munich.
Furthermore, in Mourinho - who is sure to face a hostile reception from a partisan crowd following his tenure in charge of rivals Real Madrid - Chelsea have a coach who is looking to create history by becoming the first man to triumph in the Champions League with three different teams, following successes with Porto and Inter.
Indeed, Chelsea's progression to the final four was equally as impressive as Atleti's, as the Stamford Bridge outfit defeated Ligue 1 champions Paris Saint-Germain 2-0 on home soil to overturn a 3-1 first-leg deficit and progress on away goals.
If Chelsea are to leave the Spanish capital with a first-leg victory, they will do so without suspended defender Branislav Ivanovic, while attacker Eden Hazard remains a doubt with a calf problem.
Intriguingly, on-loan Chelsea goalkeeper Thibaut Courtois is set to face his parent club, with the question of his availability the cause of much controversy following the semi-final draw.
Elsewhere, the Rojiblancos will monitor the fitness of winger Arda Turan, who has recently returned to training following a groin injury.
Atletico Madrid: Courtois; Juanfran, Miranda, Godin, Luis; Garcia, Gabi, Tiago, Koke; Costa, Villa.
Chelsea: Cech; Azpilicueta, Cahill, Terry, Cole; Lampard, Luiz; Willian, Oscar, Schurrle; Torres.