Chelsea host PSG in the last 16 second leg clash with a slight advantage on away goals following a 1-1 draw in the first leg at the Parc des Princes.
Luiz joined PSG from Chelsea in a £50 million move in June last year, vacating the Chelsea backline to join Brazilian compatriot Thiago Silva at the heart of Laurent Blanc's defence.
Mourinho's men boast the second best defensive record in the Premier League, having conceded just 22 league goals, and have let in just four in the Champions League.
But Luiz - who recently claimed Mourinho is "not special" - told The Mirror: "I know how Jose will prepare for this, he will be telling the boys to be patient and hit us on the counter-attack.
"He knows that we need to score and that they don't, I know that is his way. We must be careful because I know that Chelsea have the ability to hurt on the counter attack, but they must be careful as well.
"To sit back and just defend against Zlatan [Ibrahimovic], [Edinson] Cavani and [Ezequiel] Lavezzi can also be very dangerous, so it is not just us who have to be careful.
"It is important we believe we can win, and the team think we can. I thought we were the better team in Paris.
"If Chelsea did not have [Thibaut] Courtois in goal we would have won the game. He was unbelievable, it is clear that Chelsea have one of the best goalkeepers in the world.
"Stamford Bridge is a big weapon for Chelsea, they are very strong there.
"It is not often they lose there, but this is a special Champions League night and we must believe we can go and get a positive result.
"We have players that are used to big occasions, and playing in big stadiums, we know we can do this."
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