The Liberty Stadium last-32 first-leg clash sees Swansea boss Monk face an intriguing head-to-head with revered Napoli chief Rafa Benitez.
While Monk's coaching reign has spanned just three games since he succeeded Michael Laudrup in the Swansea hot-seat, Benitez's record is one laced with success and silverware.
"Of course, I never excepted to be in this position," Monk said.
"I was a player going into training one moment, then taking charge of games we have had already like the (south Wales) derby, and now against Napoli, so it's a whirlwind.
"But I am prepared. I am a level-headed lad, I know what I want to do.
"Napoli are one of the best teams in Europe. I have seen a lot of their games and studied them. They have good players all over the pitch.
"At this moment in time they are one of the most powerful clubs in terms of what they can spend and the quality of players they have, so we are in for a tough time, but it is a game we are really looking forward to.
"We are under no illusions how tough it will be, but if players can concentrate on themselves and be at their best, that is all we can do."
Swansea have beaten Cardiff and drawn at Stoke in the Barclays Premier League since Monk took charge, with their solitary defeat being last Sunday's FA Cup fifth-round loss against Everton.
Monk made a number of changes for the Goodison Park trip, and while it is likely he will revert to a more familiar line-up against Napoli, there will be no return from injury for star striker Michu at this stage following ankle surgery in December.
"It's been difficult," Monk added. "He came back into training, but he is still feeling soreness. We had to pull him out of training and he has to have an injection.
"It's nothing serious, but he needs two days' complete rest and we can build him up. He won't be available (on Thursday), which is disappointing for him and us. He was eager to get out there, but sometimes you can push yourself too much.
"Whatever team is picked is one I think can win the game. When a new manager comes in it is a fresh slate, and I've said there are so many games everybody will play, and that's the truth. I can only pick a side which I think can win a game, and that will be the case on Thursday.
"The priority is staying in the Premier League, that is fundamental for the club, but nights like this don't come around very often.
"We want to put on a performance we can be proud of. That is the mentality I've had since I have come in, and we will take it into this game.
"We are up against a very good side, but we believe in ourselves and we will let them know they are in for a game.
"They (Napoli) will be strong no matter who they put out, and I am sure sure they will go as strong as they can even if he (Benitez) rotates international players throughout the squad.
"It will be good to speak to him afterwards to pick his brain after being in the job for 10 days. It will be nice if we have the right result first, but someone of that experience and stature is someone to aspire to and I can take him as an inspiration."