Both teams go into the final Group F match in Naples looking to progress to the knockout stages of the competition.
Arsenal have the upper hand as they lead the pool, three points clear of nearest rivals Borussia Dortmund and Napoli.
Napoli are third, level on nine points with Borussia, and need to either beat Arsenal by a 3-0 margin or better the result of the German outfit, who visit bottom-side Olympique Marseille in the other pool game.
"We know that Arsenal are very strong but we will try," Benitez said in Tuesday's press conference. "My team has to give 100 per cent.
"My players know how important tomorrow's game is and they have all trained really well.
"We have nothing to lose.
"For us to play at home gives us an added strength.
"We were unlucky to be placed in such a difficult group but for me, it's better to experience these games rather than watch them on TV."
Benitez, whose side is third in Serie A, believes the key will be for his side to score an early goal.
"We will try to score as soon as possible and then we will see what the other result is in the other (group) game," he said.
"The result between Olympique and Borussia Dortmund can help us but the message I have given to my players is to focus on ourselves.
"We will go out determined to win by either scoring one or more goals.
"If they (Arsenal) score one then we will need to score four.
"However, while we have to play attacking football, we have to do that showing the right balance."
The former Liverpool tactician knows his team faces a huge task against an Arsenal side that have looked solid this season.
The Gunners, who were held to a 1-1 draw by Everton on Sunday, lead the Premier League standings with a five-point advantage over Liverpool and Chelsea with 15 games played.
Moreover, Arsene Wenger's men have lost just once in Europe this season, a 2-1 defeat to Borussia Dortmund back in October.
"In modern football everyone knows the quality of their rivals," Benitez said. "Arsenal is a very strong side.
"This could be the year they win the Premier League.
"For me Wenger is the best coach in the Premier League and knows what his team must do.
"Arsenal will try to control possession and hit us with counter attacks. We have to do our thing, focus on ourselves and not on them."
Benitez will be hoping to recover Spanish goalkeeper Pepe Reina, who missed Saturday's 3-3 draw against Udinese with a muscular injury.
"We will evaluate Pepe and Valon's condition tomorrow," Benitez said.
Should Reina fail to recover, Rafael will take his place in goal. Moreover, midfielder Valon Behrami is doubtful with a foot injury while playmaker Marek Hamsik is out with a foot problem.
Goran Pandev, who struck a brace in just three minutes against Udinese, will partner Gonzalo Higuain up front.
Higuain turned 26 on Tuesday and is Napoli's top scorer in the Champions League with three goals netted.
"We know it's going to a very tough game and we know Arsenal's value," Higuain said. "But we know that we can play against anyone and do well.
"We have already beaten Borussia and Marseille at the San Paolo stadium."