Apart from Pep Guardiola, who has won eight and lost four of his meetings with Mourinho during spells with Barcelona, Bayern Munich and now Manchester City, Mourinho has more often than not proved a thorn in the side of most of his rivals.
Arsenal manager Arsene Wenger took 13 years to finally enjoy a Premier League win over the Portuguese, at the 13th attempt.
The uber-confident Klopp, however, will suffer no such inferiority complex.
He has locked horns with the Portuguese seven times since he was in charge of Borussia Dortmund and Mourinho was at Real Madrid. Only once has he suffered a defeat and even on that occasion Dortmund still knocked Madrid out in the UEFA Champions League semi-finals 4-3 on aggregate.
Klopp has three wins to his name with three other games against Mourinho ending in draws - including both Premier League meetings last season during Mourinho's first season at the Old Trafford helm having replaced Louis van Gaal.
The charismatic German has clearly enjoyed pitting his wits against Mourinho on the pitch and while there is a healthy respect between them, there is also an edge that this weekend's north west showdown is likely to sharpen.
During the draw at Old Trafford in January the managers confronted each other in the technical area with Mourinho suggesting afterwards that Klopp concentrate on coaching his team rather than waving his arms about.
Klopp hit out at United's 'long-ball' tactics.
The presence of Klopp and Mourinho in rival dugouts adds another level of intrigue to a fixture between two clubs with 38 league English titles between.
Since Mourinho was appointed as United's manager he has earned 88 points, exactly the same as Klopp in the same period.
Yet Mourinho has two major trophies in the bag - the League Cup and UEFA Europa League - while Klopp awaits his first.
Mourinho said he is relishing another meeting with a club against who he claimed his first trophy in English football when Chelsea beat Liverpool in the 2005 League Cup final but against whom he suffered two Champions League semi-final defeats.
"At Anfield I've had great moments and I've had bad moments," he said. "They have had happiness against me, they have had very sad moments against me.
"(Now) if they respect me as much as I respect them, we are going to have another one of those matches."