Two weeks ago Roy Hodgson took a weakened side to the Stadio San Paolo and earned a creditable goalless draw.
The Reds boss has promised to field a stronger team for the home clash in Group K and Mazzarri expects a more difficult challenge.
"Playing Liverpool means a great deal. We've played that first game now, we're at Anfield now in a stadium full of history and it is a source of great pride for our team just to be here," he said.
"We know it is going to be difficult but games are often decided by small incidents on the pitch.
"We need to be extremely focused, concentrate on our own game and also try to restrict the great players we will be up against tomorrow.
"We played Liverpool two weeks ago and we didn't lose so we are equal.
"It is one thing to say we are equipped to deal with Liverpool but another thing to actually do it.
"They are a big top team, even when they don't have their first XI playing, but I think the fact they came to San Paolo and adopted a cautious approach suggests they were a little bit worried, and so maybe we are starting to build a reputation in Europe."
Since the two clubs drew 0-0 in Naples a fortnight ago Liverpool have received a boost, winning both their Barclays Premier League matches.
Napoli, fourth in Serie A, lost at home to AC Milan immediately after facing Hodgson's side but bounced back on Sunday with a 1-0 win at Brescia.
They have lost only one of their last five away matches in Europe but have drawn all three of their Group K games.
Mazzarri accepts they need to find a win from somewhere to aid their progress into the knockout stage.
"We have played three games and got three draws so if we do well then that gives us a lot of confidence but regardless of the result we are going to have to try to move on in the next two matches.
"It would appear Liverpool have got back some of their better players and are in good form so we know we will have to put in a good performance."
Slovakia midfielder Marek Hamsik has been linked with a move to the Barclays Premier League but dismissed suggestions tomorrow was a chance for him to showcase his qualities to a number of suitors expected to be in the crowd.
"This isn't really about individuals, it is about the group and it is an important game for Napoli," said the 23-year-old.
"It will be difficult because when you play in Europe there are no easy games.
"I know the Premier League is a great league and has a wonderful atmosphere.
"At the moment there are rumours (about him) and that is all. I'm quite relaxed about the situation and I just want to play well for Napoli.
"These kind of games help us to grow and mature as players."