The hosts reached the quarter-finals of last year's competition, while their visitors dropped out of their group and into an unsuccessful Europa League playoff bid.
Match preview
Benfica earned a place in the 2023-24 Champions League group stage after winning the 38th Primeira Liga title in their history last time around, and Roger Schmidt's side set their sights on another impressive continental run after reaching the quarter-finals of Europe's premier competition last time around.
As Aguias were handed a tough group alongside Paris Saint-Germain, Juventus and Maccabi Haifa, and they progressed in first place with an unbeaten record, having picked up four victories and played out two draws in the fixtures against French giants PSG.
That top-spot finish booked the Portuguese outfit a round-of-16 tie with Club Brugge, and they progressed in style with a 7-1 aggregate victory, including a 5-0 thrashing at the Estadio da Luz, only to fall just short in the quarter-finals, dropping out at the hands of eventual runners-up Inter Milan following a 5-3 defeat over two legs.
They now head into the start of the new group stage having played five games of their league title defence thus far, after triumphing over rivals Porto in the Supertaca Candido de Oliveira, with Schmidt's men having suffered a losing start against Boavista before putting four straight victories together to establish themselves in the Primeira Liga's leading pack, most recently following up a 4-0 thrashing of Vitoria de Guimaraes with a 2-1 win over Vizela on Saturday, thanks to Petar Musa's opener and Angel Di Maria's 39th-minute free-kick.
They will now aim to carry that momentum into their group opener on Wednesday and make a winning start on home turf before meeting Inter Milan and Real Sociedad next month.
They meet a Red Bull Salzburg side who will also look to start on the front foot in their bid to reach the Champions League knockout stage for just the second time in their history, after falling short of qualifying last year.
The Austrian outfit found themselves in a group with Chelsea, AC Milan and Dinamo Zagreb, and their tally of six points was not enough to book a round-of-16 place, as they instead finished third and dropped into the Europa League playoff round as a result.
A tie with Roma awaited, and Die Roten Bullen fell just short, despite winning their home leg, as they eventually suffered a 2-1 defeat to the eventual finalists and missed out on another round of 16.
Under the new management of Gerhard Struber, Red Bull Salzburg have enjoyed a fine start to the new term, in their bid to win an 11th straight Austrian Bundesliga title, starting with six consecutive victories, scoring 16 goals and only conceding twice in the process, before dropping points for the first time this campaign in a 2-2 draw away at Sturm Graz on Saturday, having earned a share of the spoils thanks to Sekou Koita's 73rd-minute penalty after Samson Baidoo had initially put them ahead.
Now turning their attention away from the league for the first time of the season, Struber's men will travel to the Estadio da Luz with the aim of taking a major scalp and starting with a positive result before hosting Real Sociedad in the second round of group fixtures.
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Team News
Roger Schmidt may opt to deploy an unchanged Benfica starting XI from their league triumph at the weekend, with Anatoliy Trubin again set to start between the sticks, having earned his debut for the club against Vizela after arriving from Shakhtar Donetsk to replace departing stopper Odysseas Vlachodimos.
Fellow summer signing Angel Di Maria has already made a major impact in Lisbon, with the 35-year-old having contributed five goals and two assists in six appearances across Primeira Liga and Supertaca action since returning to the club after 13 years away with Real Madrid, Manchester United, Paris Saint-Germain and Juventus.
He will line up on the right wing, with Joao Mario set to operate on the other flank in support of lone striker Petar Musa, while Joao Neves and new arrival Orkun Kokcu will continue to partner up in the engine room with 19-year-old Antonio Silva joining veteran Nicolas Otamendi at the back.
Red Bull Salzburg's attack on Wednesday should be spearheaded by 19-year-old Karim Konate, who has already managed six goals and two assists in eight appearances across league and cup action so far this term, and 20-year-old Roko Simic, who opened his account for the campaign with a brace in a recent 2-0 beating of Rapid Vienna, although Sekou Koita does also have a claim to come in from the start up front, having moved onto three goals for the season with his equaliser off the bench at the weekend.
Whichever two forwards are deployed will have support from Israeli prospect Oscar Gloukh, who has chipped in with a goal and three assists so far this campaign, while Maurits Kjaergaard, Mads Bidstrup and Lucas Gourna-Douath should all keep their places in the engine room.
Key defender Strahinja Pavlovic missed the recent Sturm Graz contest through illness, and if he is not deemed ready to return in time for Wednesday's trip to Portugal, Kamil Piatkowski and Samson Baidoo should again partner up at the heart of the defence in front of stopper Alexander Schlager.
Benfica possible starting lineup:
Trubin; Bah, Silva, Otamendi, Aursnes; Neves, Kokcu; Di Maria, Silva, Mario; Musa
Red Bull Salzburg possible starting lineup:
Schlager; Dedic, Piatkowski, Baidoo, Terzic; Bidstrup, Gourna-Douath, Kjaergaard; Gloukh; Konate, Simic