The Portuguese, who spent three seasons with Real, can become the first manager to lift the Champions League three times, but faces a stern test in the form of the Liga leaders
The Portuguese cut a frustrated figure as he witnessed his Chelsea side lose ground in the Premier League title race in a 2-1 setback to Sunderland on Saturday, a defeat that saw Mourinho's 77-match unbeaten league run at Stamford Bridge come to an end.
|5/6||Chelsea are 5/6 with William Hill to qualify for the Champions League final|
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. Their form has had a lot to do with the sensational form of Thibaut Courtois, the goalkeeper, intriguingly, on loan from Chelsea.
His availibility has been the source of much debate but he is set to feature against his parent club - Uefa rules do not forbid it - while Diego Costa, a summer target for Mourinho, will also play.
Costa has scored seven goals in six Champions League games this season and could deliver a hammer blow to the Blues' chances of lifting the trophy this season, before joining the west Londoners in the summer.
Atletico ensured they would feature in their first semi-final in Europe's premier competition since 1974 as they overcame Barca 2-1 on aggregate and quelled the threat of Lionel Messi.
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 manager 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.
Atleti will also monitor the fitness of winger Arda Turan, who has recently returned to training following a groin injury.