The Saints, who are just two points behind the Blues in the Premier League table, travel to Stamford Bridge on Sunday, when the pair will come up against each other for the first time in English football.
They were on opposite benches four times in La Liga, with Mourinho's Real Madrid defeating Pochettino's Espanyol on each occasion, but the Southampton chief is looking forward to his fresh start against the Portuguese coach, whom he values as a friend and rates as a legend of football management.
"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," Pochettino told reporters.
"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 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."
Mourinho has won seven domestic titles across four European Leagues, and the Champions League with two different clubs, during his career in the dugout, which began at Benfica in 2000.