Tim Matavž scored a hat-trick as PSV Eindhoven came from behind to inflict a first European home defeat on SSC Napoli since December 1994.
Assured of second spot in UEFA Europa League Group F, the Partenopei were on course to avenge their matchday two loss to PSV when Edinson Cavani rolled in his competition-leading seventh goal of the campaign. Matavž, however, ensured that the Dutch side bowed out on a positive note, putting the visitors ahead before the break with two close-range efforts and sealing Napoli's first continental loss at the Stadio San Paolo in 15 games on the hour.
With nothing but pride on the line for both teams, it was no surprise that the contest was an open affair. The Azzurri threatened through both Bruno Uvini, with a header, and Eduardo Vargas, before Cavani's 18th-minute strike.
PSV contributed to their undoping, with Mathias Jørgensen playing a pass into Peter van Ooijen, who was facing his own goal. Under pressure from Marco Donadel, Van Ooijen could only watch in dismay as the ball reached Cavani, whose finish was unerring.
By half-time, though, Napoli were behind to a pair of poacher's finishes from Matavž, who on both occasions followed up to punish Antonio Rosati for handling errors. His first came in the wake of Van Ooijen's curling shot and the second after Jeremain Lens had chanced his arm.
With their proud home record under threat, Walter Mazzarri's team surged forward, Andrea Dossena testing Boy Waterman and then firing the rebound wide. After the restart, Rosati partially redeemed himself by tipping away a Georginio Wijnaldum effort.
Back came the Serie A side and seconds after Waterman had thwarted Christian Maggio, PSV countered with devastating effect. Matavž led the charge, squaring for Memphis Depay, who turned back inside and teed up the Slovenian international for a simple finish.