The azzurri are hoping to start what will be a challenging week on the right foot.
Napoli host Marseille in the Champions League on Wednesday before taking on Juventus in Turin next weekend.
"We have worked very hard over the last two days in view of the game against Catania, which we must face with great caution," Benitez said.
"This is our fifth game in 15 days but I see my players very concentrated and motivated.
"They are prepared to play a game that will by no means be easy."
Napoli go into the encounter at the San Paolo stadium on the back of a 2-1 win at Fiorentina on Wednesday.
That result followed their 2-0 triumph over Torino and allowed Napoli to remain in second place, five points adrift of Serie A leaders Roma and level on 25 points with Juve.
Napoli will fancy their chances of taking three points as they are unbeaten at home while Catania have lost all of their games on the road this season.
Catania suffered a blow this week with the news that striker Gonzalo Bergessio will be sidelined for two months with a fractured fibula.
Bergessio was injured in Wednesday's 4-0 defeat at Juventus.
To complicate matters for coach Luigi De Canio, midfielder Tiberio Guarante is suspended this weekend.
Catania are 18th in the standings, three points adrift of Bologna, who occupy the last position of safety.
"Against teams like Juventus and Napoli, you have to play at your very best and hope that your rivals have an off day," De Canio said.
"Unfortunately, against Juve we didn't do that."
The hosts will be without midfielder Christian Maggio, who serves a one-match ban, while defender Miguel Angel Britos and midfielder Juan Zuniga are sidelined through injury.