Whilst Mourinho was in charge of former club Real Madrid he came across Pochettino's Espanyol side on four occasions and enjoyed four wins - seeing his side score 13 goals and keep a clean sheet in every match.
Now the two meet in the Barclays Premier League for the first time as Saints travel to Stamford Bridge on Sunday afternoon and Pochettino is looking forward to pitting his wits against the so-called 'Special One' once again.
"My relationship with Jose is excellent," said the Argentinian.
"We get along very well. I have a great admiration and respect for him as a football manager and as a person and it will be great to say hello to him on Sunday and to have the game against him.
"I'm happy to be facing Jose Mourinho in England, and not in Spain. It's clear that you learn from everyone, but I've learnt a lot from Jose.
"I think he's one of the best managers in football history. His record speaks for itself. We have a very good relationship, but at the same time while before and after the games we will be friends, during the full 90 minutes we're not going to be friends, we're just going to be rivals, opponents."
Saints have been drawing the plaudits following a strong start to the current campaign but were beaten at the home of league-leaders Arsenal last weekend.
Olivier Giroud bagged a brace for the Gunners but Southampton played a part in their own downfall as goalkeeper Artur Boruc dallied on the ball before being robbed by the France forward for the opener.
The second came from the penalty spot after Jose Fonte fouled Per Mertesacker but it was the Boruc error which was highlighted as the turning point.
Pochettino defended his Polish number one and does not intend to start questioning the fluid, passing style he has introduced at the south-coast club and which has served him well so far this season - with his side sitting fifth in the table.
"As I said before, I don't see them as mistakes. I think these things can happen in football," he said.
"I don't ever really see them as mistakes. I think the feeling overall right now in the squad is a good feeling, it's a good atmosphere, but after the game the energy was quite low and we were angry and disappointed about what happened.
"We are going to continue playing the same way, we're going to continue playing with the same philosophy, with the same idea of how we execute our football.
"Because what that mistake shows is that we need to improve and we need to work even harder to improve how we play, how we reinforce that idea of quick passing of the ball and that includes Artur - that includes him in that set-up as well."