The Serie A side were drawn at home in the first leg of the play-off round tie later this month and Benitez knows Napoli must perform at the San Paolo to give them a chance of qualifying for the group stages.
A trip to the San Mames for the return game is something that Benitez is particularly concerned about, although he insists his squad have the quality to progress in the competition.
Napoli were seeded in Friday's draw and could have drawn Lille, Copenhagen, Standard Liege or Besiktas, but will face Bilbao.
"We were paired with the most difficult side of the five we could have faced, Athletic are the strongest of them all, no doubt about that," he said after the draw.
"They play good football and the great support of the 50,000 fans at the San Mames make them difficult to beat for anybody.
"I think we will see two beautiful games, played with great intensity by both sides. I think Napoli are well prepared to play a great game and reach our objective, which is playing in the group stage."
Napoli host Bilbao in the week commencing August 18 with the return leg in Spain a week later in what will be the first time the teams have faced each other in competitive action.
‘Maybe I’ll be signed by Wrexham, who knows? English football would suit me – if an offer came, I wouldn’t think twice, I’d go immediately’ Euro 2024 cult hero reveals his UK dream
‘Managing Leeds? It was an option that appeared, but it wasn’t the right timing. I decided it wasn’t a good idea to leave the club I was at mid-season’: Premier League boss admits to turning down opportunity to replace Jesse Marsch in 2023
