The hosts earned their place in this round by recording a 3-2 aggregate win over Ludogrets in round two of qualifying, while the visitors managed to overcome Zalgiris by the same aggregate scoreline.
Match preview
Olimpija lifted the Prva Liga title last season for the first time since the 2017-18 season with 73 points, which was six ahead of Celje in second place, and 11 clear of the outgoing league champions Maribor.
Joao Henriques's side were dominant in their domestic league, and despite losing their final three fixtures, they had already secured the title several weeks before the end of the season.
They beat Valmeira in the first round of qualifying and went into the last round as the underdogs but held on to a crucial 1-1 draw at Stadium Ludogorets Arena before managing a dramatic 2-1 win at this venue last week thanks to a brace from Timi Max Elsnik.
With their domestic league already underway, Olimpija lost their opening match against Koper 2-1 but bounced back with an impressive 5-0 win over Rogaska last weekend, leaving them in sixth place in the very early stages of the season.
It is worth noting that Olimpija won both their home matches against Valmeira and Ludogorets in this competition in the previous rounds and are unbeaten in their last three matches at Stadion Stozice.
Meanwhile, Turkish League champions Galatasaray will be looking to return to the Champions League main draw for the first time since the 2019-20 season when they reached the group stages fairly comfortably.
The visitors claimed their 21st Super Lig title last season with 88 points, ending the season eight points clear of Fenerbahce and on a six-match winning streak, scoring 15 goals and conceding just one in that time.
Over the course of the 36-match season, Galatasaray conceded just four defeats while recording 28 wins and four draws, and they were the best-performing away side of any team in the league.
Okan Buruk's side have only played in one previous qualifying round, which was against Bulgarian champions Ludogorets, and they were pushed all the way to the end but managed to secure a 1-0 win in the second leg after a hard-fought 2-2 draw in the first leg.
While their preseason form was nothing to write home about, Galatasaray will be the strong favourites coming into this match and will be fairly confident of securing a first-leg lead to take back to NEF Stadyumu next week.
NK Olimpija Ljubljana Champions League form:
W
W
D
W
NK Olimpija Ljubljana form (all competitions):
W
W
L
D
W
W
Galatasaray Champions League form:
D
W
Galatasaray form (all competitions):
L
W
D
L
D
W
Team News
Saar Fadida scored a hat-trick against Rogaska in the hosts last league match, and he will be hoping for a recall to the starting 11 after being left on the bench against Ludogorets.
Elsnik's goals in both legs of the last round almost guarantee that he will keep his place in the midfield alongside Agustin Doffo and Ivan Posavec.
While Galatasaray have brought in several new faces over the summer transfer window, there are several players that are ineligible to play just yet.
Among those that are yet to be registered are Kerem Demirbay, Alpaslan Ozturk, Ogulcan Caglayan and Christian Luyindama, while Nicolo Zaniolo could miss out through injury.
NK Olimpija Ljubljana possible starting lineup:
Vidovsek; Silva, Ratnik, Muhamedbegovic, Sualehe; Posavec, Doffo, Elsnik; Seslar, Nukic, Pedro
Galatasaray possible starting lineup:
Muslera; Boey, Nelsson, Bardakci, Angelino; Kutlu, Oliveira, Akturkoglu, Mertens, Akgun; Yilmaz
We say: NK Olimpija Ljubljana 1-1 Galatasaray
Based on their recent form and performances in the previous round, there is very little to choose between these sides despite Galatasaray being the out-and-out favourites to win the match. We fancy the Turkish side to qualify for the playoffs but feel that they will need to secure that win back at home with this one ending level.