The former Blues midfielder will lead the Black Cats into battle with Mourinho's men at the Stadium of Light on Wednesday evening desperately looking for a fourth successive home victory in all competitions to help ease their relegation fears.
However, while that might prove a blow to the second-placed London club's hopes of reeling in leaders Arsenal - the Gunners are currently four points better off - the 46-year-old is confident they will be involved in the mix come the end of the season.
Asked if Chelsea, who came from behind to beat Southampton 3-1 on Sunday, could go all the way as a result of Mourinho's return to Stamford Bridge, Poyet replied: "Yes, no doubt about it.
"They are different, they are stronger. The reaction at the weekend at half-time was all about the mentality of the team more than even the play or the technique or the ability.
"It was mental. It was a completely different team in the second half. I am sure there was a unique half-time team-talk in the dressing room or wherever it happened. It was a complete turn-around.
"I know him [Mourinho] and I admire him a lot. He's a different-class person and manager. I know him in football ways and as a person and I am looking forward to seeing him before the game.
"Then the game is the game and I hope everything goes all right and there are not any problems in the game between the benches.
"I had the opportunity to watch him training a few times at Chelsea and it was very impressive."
Sunderland, of course, are currently scrapping at the opposite end of the table, where they remain five points from safety despite a significant upturn in results since the Uruguayan's arrival in October.
Newcastle and Manchester City have both left Wearside pointless with the Saints also bowing out of the Capital One Cup, and while an extension of that run may sound a tall order, that is exactly what Poyet is targeting.
He said: "We know they are one of the best teams in the country and that we need to be very, very good.
"We are going to have to compete, defend well. I don't know how many chances we are going to create because they are one of the teams which defends the best in England, so there are plenty of things we need to be good at.
"But we all believe it is possible, especially after beating Manchester City at home. That shows you there is a way and hopefully we can repeat something like that."
Poyet will need all his biggest players at his disposal once again - defender John O'Shea appears to have shaken off a groin problem - if Sunderland are to stand a chance of beating the Blues, just as they did 14 years ago to the day when he ran out in the north-east into the teeth a red and white storm.
That day, first-half doubles from Niall Quinn and Kevin Phillips left Chelsea trailing 4-0 at the break, and the South American's late strike did little to ease the pain.
Poyet said: "It was one of the worst half-times I had during my time at Chelsea, if not the worst. It was embarrassing.
"For these kind of things to happen, you need two teams, two teams play a part. Maybe we were not good enough, but at the same time, Mr Quinn and Mr Phillips were on fire and they destroyed us, so it was not only us that were poor, they were very good.
"It was embarrassing, yes it was. But that shows you that when this place is full and it's a good atmosphere and the players feel it and it pushes you up and you are on a good day, anything can happen.
"We will see if we can do something special tomorrow."