Meanwhile, PSV have progressed through to this stage of the competition courtesy of topping a group which included Granada and fellow Greek side PAOK.
PSV have endured an indifferent first campaign under Roger Schmidt, the club already sitting six points adrift of Ajax having played a game more than the Eredivisie leaders.
However, the Dutch outfit overcame a slow start in this competition to book their place in the last 32, winning their final three games to edge out Granada for top spot.
PSV warmed up for the trip to Greece with a shock 2-2 draw away at ADO Den Haag after conceding a last-minute equaliser to their relegation-threatened opponents.
On a positive note, Donyell Malen posted his second double in three matches, taking his tally for the season to 19 goals in all competitions.
Olympiacos would have fancied their chances of still being in the Champions League at this stage of the season when they defeated Marseille on matchday one.
However, five successive defeats followed for Pedro Martins's team, their place in the Europa League only being secured when Marseille lost out at Manchester City in their final game.
Martins will be the first to acknowledge that the club are fortunate to be still competing on the continent, as well as being provided with a winnable tie.
Nevertheless, Olympiakos, the Greek league leaders, had been on a 15-match unbeaten run in all competitions before they succumbed to a 2-1 defeat at Panathinaikos on Sunday.
Olympiacos Champions League form: WLLLLL
Olympiacos form (all competitions): WWWWWL
PSV Eindhoven Europa League form: LWLWWW
PSV Eindhoven form (all competitions): WWLWLD
Schmidt is expected to make a number of changes to his PSV starting lineup, including handing a recall to Denzel Dumfries.
Veteran forward Youssef El-Arabi will also expect to return to the team after only being named as a substitute against Panathinaikos, likely leaving Koka to take a place on the bench.
Giorgos Masouras is another creative player in contention to come back into the side.
Olympiacos possible starting lineup:
Sa; Androutsos, Sokratis, Ba, Reabciuk; Silva, Camara, Bouchalakis; Vrousai, El-Arabi, Masouras
PSV Eindhoven possible starting lineup:
Mvogo; Dumfries, Teze, Boscagli, Max; Sangare, Rosario; Thomas, Vertessen; Zahavi, Malen
We say: Olympiacos 1-2 PSV Eindhoven
After their poor European form during the first half of the campaign, Olympiacos will be motivated to go deep in this competition. However, PSV may have too much quality in attack, putting them in a position to net important away goals ahead of the second leg.