The top of the table clash kicked off at the Stadio Diego Armando Maradona this evening at 19.45 GMT.
Football fans were surprised to see that seated next to President De Laurentiis was rock icon Patti Smith.
She is in town after performing a concert and also posted images of her wander around the streets of Naples on Instagram, including some Kvicha Kvaratskhelia graffiti and the celebratory banners marking the Scudetto victory.
Sat behind them was former Napoli captain Insigne, who is reportedly pushing for a return to Italy after his disappointing MLS experience at Toronto FC.
His presence probably added to the sense of deja-vu for Walter Mazzarri, who was making his first appearance on the Napoli bench in 10 years.
When he was last the coach, it was still called the Stadio San Paolo.