Both teams were beaten on the first matchday of the competition, leaving them third and fourth in the Group F table respectively.
The Gunners have had mixed results in the Premier League since that defeat, losing 2-0 to Chelsea before beating Leicester City in high-scoring match at the King Power Stadium last weekend.
While Arsenal have been short of strikers in the opening weeks of the season, Theo Walcott has scored in three of the team's last four matches, while Alexis Sanchez netted a hat-trick in the win over Leicester.
Arsene Wenger's side have been eliminated from the Champions League in the round of 16 for the last five seasons, being knocked out on away goals by AS Monaco last year after the two-legged tie finished 3-3.
Arsenal were the runners-up in the group stage last season, losing just one of their six fixtures while scoring 15 goals, but conceding eight - twice as many as Borussia Dortmund, who finished top.
Recent form: DWWLWL
Recent form (all competitions): WWLLWW
Olympiacos were comfortably beaten by Bayern Munich in their opening match in Group F, slipping to a 3-0 defeat to the Bundesliga champions.
The defeat is the Greek side's only loss so far this season, as the club have a 100% record from their first five outings in the league, including an emphatic 5-1 victory over PAS Giannina at the weekend.
It was a summer of change for the Greek club, having appointed Marco Silva as manager in July. There were also a string of new signings, including midfielder Pajtim Kasami from Fulham, Leicester City's Esteban Cambiasso and striker Brown Ideye from West Bromwich Albion.
Kostas Fortunis, who is in his second season with the club, has made a bright start to the season, scoring five goals in six appearances for the team.
Olympiacos have reached the knockout stage of the Champions League just once since 2010, while reaching the round of 32 in the Europa League last year.
The team narrowly missed out on a place in the round of 16 last year, finishing just a point behind Juventus in their group, with three wins and three losses from their six fixtures.
Recent form: LWLLWL
Recent form (all competitions): WWWLWW
Having been sent off in the defeat to Zagreb earlier this month, Olivier Giroud is suspended for the home side, leaving the Gunners short up front.
The visitors also have a player suspended as Luka Milivojevic is still serving a ban from last season, while Andreas Bouchalakis misses out with a thigh injury and Giannis Maniatis is still working on regaining match fitness following a lengthy absence with a knee problem.
Manuel da Costa will need a late fitness test after picking up a calf injury, while Alejandro Dominguez is working to overcome a thigh strain.
Arsenal possible starting lineup:
Martinez, Monreal, Koscielny, Mertesacker, Bellerin, Coquelin, Ramsey, Ozil, Sanchez, Oxlade-Chamberlain, Walcott
Olympiacos possible starting lineup:
Roberto, Elabdellaoui, Botia, Siovas, Masuaku, Cambiasso, Salino, Kasami, Fortounis, Pardo, Ideye
Head To Head
This is the fourth time since 2009 that these two clubs have been drawn in the same group in the Champions League, having most recently met during the 2012-13 campaign.
In their last match, Olympiacos secured a 2-1 win, having been beaten 3-1 by Arsenal at the Emirates two months earlier.
In six meetings between the two sides in the Champions League, the home side has always secured the win, while Arsenal have scored nine goals to Olympiacos's eight in their previous matches.
We say: Arsenal 2-1 Olympiacos
Although Olympiacos have been in stronger form domestically, the head-to-head record suggests that a win for the hosts is the most likely outcome. The Greek side have not faced any of their title rivals so far in the league, and they struggled in the second half of their match against Bayern a couple of weeks ago.