Napoli will play against the winner of the other semi-final, which takes place this Friday, between Bologna, winner of the Coppa Italia, and the runner-up of Serie A, Inter Milan.
Napoli star Rasmus Højlund shone as the defending Serie A champion defeated AC Milan 2-0 on Thursday to reach the final of the Supercoppa Italiana.
The former Manchester United player assisted on one goal and scored another to lead Napoli to the final on Monday.