Either Zrinjski or Sheriff Tiraspol will await the victors in round two, while the losers will drop into the third round of Europa Conference League Qualifying.
Ending a three-year drought without a top-flight title to their name, Slovenian powerhouses Maribor edged out Koper by three points to win their 16th PrvaLiga honour in the 2021-22 season and earn another opportunity to dine with the European elite.
Maribor are no strangers to facing the best that the continent has to offer, having reached the Champions League group stages three times down the years - most recently in 2017-18 - and they have never been eliminated in the first round of Champions League Qualifying before.
However, the Violets' most recent attempt to make a name for themselves on the continent saw them lose to Coleraine in the first round of 2020-21 Europa League Qualifying, and their pre-season period under Radovan Karanovic has been anything but smooth sailing.
Indeed, the Slovenian champions won just one of their five pre-season friendly fixtures in June and failed to win any of their four exhibition matches at home - drawing each of their last three - so channelling the spirits of their previous European hopefuls is a must here.
Over in Belarus, Shakhtyor have already kicked off their quest to win a third successive top-flight title after coming up trumps in 2020 and 2021, winning last season's crown by a 10-point margin over closest challengers BATE Borisov.
The 2022 Belarusian Premier League season is in full swing, but the reigning champions are already fighting an uphill battle to keep their hands on the silverware, languishing in fifth in the table and seven points adrift of BATE with a game in hand.
Sergey Tashuev - who only took the reins in April - oversaw a 1-0 loss to Torpede BelAZ in their most recent fixture on June 25, but Shakhtyor will at least have the benefit of a full week's break in between their two legs with Maribor after their scheduled league showdown with Slutsk was postponed.
The visitors have only appeared in Champions League Qualifying twice before, and both times they were eliminated in the first round, losing 2-0 on aggregate to Ludogorets last year after going down by the same scoreline to Siroki Brijeg in 2006.
All four of Shakhtyor's Champions League Qualifying games so far have ended in a 1-0 defeat, and breaking that scoreless streak at the fifth time of asking will be firmly on the minds of Tashuev's crop on Wednesday.
Maribor do not have any injury woes to contend with following the pre-season period but have waved goodbye to a club legend in Marcos Tavares, who has retired after 14 years and nine top-flight titles with the Violets.
Tavares left the club as their all-time top goalscorer and appearance maker with 211 strikes in 593 matches, and Karanovic has also seen Ognjen Mudrinski leave the club on a free transfer.
Thirty-eight-year-old Tavares featured alongside his son and namesake Marcos Tavares in the 2021-22 season, but the 18-year-old has not been named in the hosts' squad for this game.
Meanwhile, Shakhtyor midfielder Nikita Korzun received his marching orders late on against Torpedo last time out, but the 27-year-old is fine to take his place in the 4-2-3-1 formation for Wednesday.
Maribor possible starting lineup:
Bergsen; Milec, Mitrovic, Watson, Sikosek; Repas, Makoumbou; Zugelj, Kronaveter, Brnic; Baturina
Shakhtyor Soligorsk possible starting lineup:
Plotnikov; Shevchenko, Satara, Politevich, Antic; Korzun, Divanovic; I. Ivanovic, Ahmedi, Podstrelov; Darboe
We say: Maribor 2-1 Shakhtyor Soligorsk
Shakhtyor have already tasted competitive action this summer, which could certainly work in their favour against a Maribor side who flattered to deceive in the pre-season period.
The hosts' European pedigree certainly outweighs that of Tashuev's side, who have been far from perfect in the 2022 Belarusian top flight so far, and we have faith in Maribor to travel to Soligorsk with a slender lead in tow.
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