The Irish side will be looking to make the most of home advantage on Tuesday before they head to Malta next week for the return leg.
Shamrock Rovers will be hoping to translate their domestic form into European action, with the hosts currently 10 points clear at the top of the League of Ireland Premier table.
A Rory Gaffney goal in first-half stoppage time of Friday's contest against Finn Harps ensured that Shamrock Rovers have emerged victorious from their previous three competitive games.
With the Irish champions currently enjoying a fine run of form, they will be hopeful of bettering last year's Champions League first-round qualifying exit.
Slovan Bratislava got the better of Shamrock Rovers on that occasion, resulting in the Irish side dropping down to the Europa Conference League where they progressed to the playoff round before losing to Flora.
Although they lost to Slovan Bratislava last season, Shamrock Rovers managed to pick up a 2-1 home victory before losing 2-0 in the away leg, which gives the hosts a chance to claim consecutive home victories in the Champions League.
Like their hosts, Hibernians were also eliminated in the first round of Champions League qualifying last season after losing 5-0 on aggregate to Flora.
They dropped down to the Europa Conference League where they beat Folgore before losing to Riga in the third round of qualifying.
With their domestic season not currently underway, the Maltese Champions will have to get up to speed quickly if they are to get the better of Shamrock Rovers.
Preparations for the first leg have been less than ideal, with their two friendly fixtures against fellow Maltese opposition resulting in a 2-1 defeat and a 2-2 draw against Floriana and Gzira respectively.
Tuesday's contest represents their first meeting against Shamrock Rovers, and the visitors are tasked with becoming the first team since August 2021 to beat the Irish champions on home turf.
Shamrock Rovers could be without the services of Jack Byrne, who has been out since May due to a calf problem.
Richie Towell could come into the starting lineup after making his return from injury with a second-half appearance in Friday's win over Finn Harps.
Terence Groothusen has also signed for the club, and the 25-year-old could lead the line for the visitors in the first leg.
Malta international Jurgen Degabriele will be crucial for his side after top-scoring in the league for Hibernians last season.
Shamrock Rovers possible starting lineup:
Mannus; Hoare, Lopes, Grace; Gannon, Towell, O'Neill, Kavanagh; Greene, Watts, Gaffney
Hibernians possible starting lineup:
Cremona; Z. Grech, Fonseca, Agius, Lauresen, Izquier; Thaylor, J. Grech, Vella, Degabriele; Groothusen
We say: Shamrock Rovers 2-0 Hibernians
Shamrock Rovers tend to perform well on home turf, and with the hosts over halfway through their domestic campaign, we think that they will be better prepared to claim a first leg win than the Hibernians who have played two friendlies in preparation for Tuesday's contest.
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