Only 10 miles separate the Super League side's home ground from the AEK Arena, but their Italian counterparts will try to spoil the party by going one better than a painful loss in Prague 12 months ago.
Match preview
By taking apart Premier League high-flyers Aston Villa in the semi-finals, ultimately cruising to 6-2 aggregate win, Olympiacos booked their place in a showpiece with special resonance for the Piraeus club's fans, who will not travel far to attend their team's first UEFA final.
The Erythroleykoi had edged past Maccabi Tel Aviv and Fenerbahce in the previous two rounds - spectacularly beating the former after extra time and then the latter on penalties - but a masterclass from Moroccan striker Ayoub El Kaabi sealed his side's place in this week's decider.
Having found the net no fewer than five times versus Villa, El Kaabi moved on to 15 goals in continental competition this season - more than any African footballer has ever managed in a single European campaign - and he has come to symbolise the unlikely progress of Olympiacos in 2024.
Experienced coach Jose Luis Mendilibar was appointed in mid-February, following Carlos Carvalhal's departure, and the Basque boss has taken his new club to within one game of replicating last year's remarkable feat - leading a struggling Sevilla side to yet another Europa League title.
On this occasion, Mendilibar has already helped Olympiacos become only the second Greek outfit to reach a UEFA final, some 64 years since their debut in European competition.
With Wednesday's game taking place more or less in their own back yard, a unique kind of pressure will apply to the squad that has just finished third in the Greek Super League, following a 2-2 draw with arch-rivals Panathinaikos in their final domestic fixture.
They are the first club to contest a European final in their home country since Marseille lost the 2018 Europa League decider to Atletico Madrid, and each of the last four teams to do so have all ended as runners-up.
While their rivals for the Conference League trophy dropped into UEFA's third-tier tournament after exiting the Europa League, Fiorentina came through qualifying for the second straight season to earn their shot at redemption.
Beaten by Jarrod Bowen's 90th-minute winner for West Ham United this time last year, the Viola are determined to bring silverware back home to Florence, bagging a bonus place in next term's new-look Europa League in the process.
En route to Athens, the Serie A side are unbeaten in 13 European matches - the longest such run in their long history - having progressed through the playoff round before topping Group F last autumn.
Throughout the knockout phase, Fiorentina have pushed their luck, following a stoppage-time winner against Maccabi Haifa in the last 16 with an extra-time victory over Viktoria Plzen; then, Lucas Beltran's late penalty sunk Club Brugge in the semi-finals.
Vincenzo Italiano's penultimate game in charge - his team must still meet Europa League winners Atalanta BC in a potentially celebratory final fixture, delayed until Sunday due to both sides' busy schedules - offers the chance to shake off claims he cannot cut it on the big stage.
A highly-regarded tactician, Italiano lost last season's Coppa Italia and Conference League finals, before dramatically exiting to Atalanta in the cup semis this season, so he will have something to prove on Wednesday night - particularly as his team have just finished eighth in the Serie A standings.
Last year's loss in Prague was Fiorentina's fourth defeat in five continental deciders to date, leaving the Tuscan club with only the 1961 European Cup Winners' Cup to show for their efforts; therefore, Olympiacos will not be the only team under pressure to claim victory in the Greek capital.
Olympiacos Europa Conference League form:
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Olympiacos form (all competitions):
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Fiorentina Europa Conference League form:
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Fiorentina form (all competitions):
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Team News
Benefiting from over a week of preparation time, Olympiacos coach Jose Luis Mendilibar will have all his main men available for Wednesday's final, including ex-Fiorentina forward Stevan Jovetic, who was recently sidelined by injury.
Scorer of 40 goals in 135 appearances for the Viola between 2008 and 2013, Jovetic struck late on to secure Europa Conference League qualification in the Super League derby draw with Panathinaikos. However, he is unlikely to start against his former club.
Daniel Podence - who was sent off last time out - and Kostas Fortounis should instead support star striker Ayoub El Kaabi in the final third; the latter is top scorer across all European competitions this season, including 10 goals in the knockout stages thus far.
Goalkeeper Konstantinos Tzolakis recently received his first senior call-up for Greece, and national team defender Panagiotis Retsos is set to partner David Carmo at the back.
Only Nelson Abbey and Gelson Martins will miss out, as neither was included on the Piraeus club's UEFA squad list; meanwhile, Fiorentina's sole absentee is winger Riccardo Sottil, who fractured his collarbone earlier this month.
As mercurial as many of his frustrating forward players, Vincenzo Italiano has named the same starting XI in back-to-back games just once during three years at the club, so his selection could contain some surprises.
In the Viola's latest outing - where they spoiled Claudio Ranieri's emotional send-off by beating Cagliari 3-2 in Sardinia - regular starters such as Nico Gonzalez, Arthur, Lucas Beltran and Christian Kouame were all rested.
However, Antonin Barak and Jonathan Ikone are expected to drop back down to the bench, making way for more familiar faces.
Beltran is Fiorentina's leading goalscorer in the Conference League this term, with four goals - including a crucial spot-kick in Bruges to win their semi-final tie - and he will most likely link up with either Andrea Belotti or the rejuvenated M'Bala Nzola in attack.
Olympiacos possible starting lineup:
Tzolakis; Rodinei, Retsos, Carmo, Quini; Hezze, Iborra; Fortounis, Chiquinho, Podence; El Kaabi
Fiorentina possible starting lineup:
Terracciano; Dodo, Milenkovic, Martinez Quarta, Biraghi; Arthur, Mandragora; Gonzalez, Beltran, Kouame; Nzola
We say: Olympiacos 2-2 Fiorentina (Olympiacos win after extra time and penalties)
Both sides have arrived in the final with a long trail of dramatic escapes and high-scoring games behind them, and there is good reason to believe that they could put on an enthralling contest.