The Special One is aiming to become the first boss to win Europe's elite club competition with three different teams.
But despite his strong record in the Champions League, Mourinho has often fallen at this hurdle before.
The Portuguese has won only twice in his previous seven semi-finals, losing the last three in succession.
As he locks horns with Simeone with the tie poised delicately at 0-0, Express Sport examines how Mourinho's sides have fared in the competition at this stage.
2003/04 (h) D 0–0. (a) W 1–0 Derlei (pen).
Brazilian striker Derlei's 60th–minute penalty puts Mourinho's Porto into the final after a tight tie.
Chelsea v Liverpool
2004/05 (h) D 0–0. (a) L 0–1.
Luis Garcia's controversial fourth–minute "ghost goal", which Mourinho still claims never crossed the line, puts his team out.
Chelsea v Liverpool
2006/07 (h) W 1–0. (a) L 0–1.
Chelsea lost 4–3 on penalties at Anfield as Pepe Reina saved from Arjen Robben and Geremi.
2009/10 (h) W 3–1. (a) L 0–1.
Tactical mastery from Mourinho as his team blitzed all–conquering Barca in Milan with goals from Wesley Sneijder, Maicon and Diego Milito, and then held out superbly at the Nou Camp.
Real Madrid v Barcelona
2010/11 (h) L 0–2. (a) D 1–1.
Pep Guardiola's revenge, as Mourinho was sent off in the first leg at the Bernabeu after Pepe's red card and Real never recovered.
Real Madrid v Bayern Munich
2011/12 (a) L 1–2. (h) W 2–1.
Real lose 3–1 on penalties after Robben's goal in Madrid sends the tie into a shoot–out.
Real Madrid V Borussia Dortmund
2012/13 (a) L 1–4. (h) W 2–0.
A disastrous first leg gave Real a mountain to climb, but they almost did it as Karim Benzema and Sergio Ramos netted. The third goal just would not come.
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