The Florence club were beaten 3-1 by Napoli in the Coppa Italia in May, having also lost 2-1 at the Stadio Artemio Franchi in the league.
Fiorentina head into this weekend's clash with the Naples outfit down in 10th place, with Montella eager to start climbing the table.
And the former Italy striker would take extra satisfaction from a victory over Benitez's side.
"Our position in the table does not reflect our ambitions," said the Fiorentina coach.
"Napoli are in good shape and we must do our best to win. Obviously we have the right hunger. Last season's defeat at home and the Coppa Italia Final still burn, so I hope the players feel the same desire to make up for those results as I do.
"Admittedly, both teams now have a few more problems than we did in May."
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