United finished second in UCL Group H under Mourinho and also expect a difficult match-up in the round of 16.
On Monday, French giants PSG were selected to face United in February. A day later, Mourinho lost his job and has since been replaced by club legend Ole Gunnar Solskjaer on an interim basis.
United’s caretaker manager will guide the team against PSG when they visit Old Trafford for the first leg on February 12.
Solskjear’s men then go to the Parc des Princes on March 6 for the return fixture.
Neymar and his team-mates have big ambitions in the competition this season and are many people’s tip to win the trophy.
PSG topped a tough Group C ahead of runners-up Liverpool and Europa League-bound Napoli.
Manchester United ultimately decided they could not move forward with Mourinho in charge with the club struggling, especially domestically.
The football has been difficult to watch for supporters, but fan-favourite and ex-United striker Solskjaer is seen as the man to bring a smile back to everyone’s faces.
PSG pose a huge test for the Red Devils next year, though, and Neymar is relishing the challenge.
He also expects United to be playing different football under Solskjaer than what he witnessed under Mourinho.
Neymar told PSG official Website:
"I was happy [with the draw]; they will be two great matches between two great sides.
"We know the quality that Manchester United have and we know that their players have a winning mentality.
"The coach has changed and it will be a different playing style - they're in the process of changing things up - but we know the quality they have.
"I love the big matches and it's always a pleasure to play in them.
“I’m very happy to be taking on Manchester United."
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