Both sides made early thrusts for a vital opener from almost the first whistle, as Daniel Podence cut inside and forced a smart save from Filippo Terracciano, before Nikola Milenkovic poked home following a corner routine, only for the goal to be ruled out for offside.
Fiorentina went on to have the better of the opening half, as Giacomo Bonaventura - who scored in last year’s Conference League final - saw a weak effort easily held by Konstantinos Tzolakis after the ball fell kindly to him in the box. And he was again denied by the goalkeeper soon after when attempting a delicate chip.
La Viola also kept Conference League top scorer Ayoub El Kaabi quiet in the first half, as a poor touch from the striker denied him a clear strike on goal.
Overall, Olympiacos would have been relieved at the 0-0 half-time scoreline, and they continued to play conservatively after the interval.
It proved effective to an extent, as Fiorentina’s next chance came on 65’, with Milenkovic heading wide from a corner. Christian Kouame, who won the AFCON title with the Ivory Coast in February, was then handed a golden opportunity to open the scoring, but his miskick was parried away by Tzolakis.
With the score still level, Olympiacos grew in confidence in the latter stages, and almost stole victory in their home country, as Vicente Iborra flicked a header just wide from substitute Andre Horta’s free-kick.
Still, the teams could not be separated after normal time, but the Greeks continued their momentum into the extended period, as substitute and ex-Fiorentina striker Stevan Jovetic saw his fierce strike tipped past the post by Terracciano.
La Viola continued to probe, and two substitutes combined in the second period of extra time, as Antonin Barak nicely set up Jonathan Ikone, but his effort could only find the palms of Tzolakis.
Olympiacos began to sense that this might be their night after that save, and with one cathartic, bursting run forward, Santiago Hezze crossed for El Kaabi to head home his 33rd goal this season to complete a Greek odyssey for the ages and gift his team their first-ever European trophy, as Fiorentina suffered heartbreak in the final once again.
Flashscore Man of the Match: Ayoub El Kaabi (Olympiacos)