Police said large groups of Italian fans engaged in "provocative behaviour" in the centre of Eindhoven on Monday night, with officers detaining 230 to prevent confrontation with locals.
Authorities questioned the Napoli fans overnight, releasing them with a fine but also banning them from the match and the city centre.
"All arrested supporters with a ticket are not allowed to attend tonight's match," said the police in a statement.
The match has been designated a "high-risk" clash, with police enforcing special rules such as preventative frisking.
Police said they would be present in large numbers ahead of the 8pm (BST) kick-off and appealed to fans to behave.
"Let's work together to ensure that tonight's game and everything surrounding it proceeds smoothly so everyone can enjoy the football match," said the statement.
On the pitch, both sides will be looking to get their Champions League campaign on track after a slow start.
Dutch champions PSV lost 3-1 at home to Union Saint-Gilloise from Belgium in their opening fixture before squeezing a 1-1 draw at Bayer Leverkusen.
Napoli lost 2-0 away to Manchester City before a 2-1 home victory against Sporting Lisbon.