Kostas Tsimikas will captain Liverpool for the first time as the Reds play Austrian side LASK in the Champions League on Tuesday.
The Greek left-back, who scored the winning penalty in the 2022 FA Cup final but spent last season out on loan with Roma, wears the armband with Virgil van Dijk on the bench.
Liverpool manager Andoni Iraola confirmed before the season that he had named Alisson Becker his vice-captain following the departures of Mohamed Salah and Andy Robertson.
But Iraola explained that the goalkeeper would never actually wear the armband on the pitch due to rules that mean only the captains can talk to the referee on the pitch.
"I explained to Alisson especially that it's not going to be possible that he wears the armband because with the new rule I think there is a big limitation if a keeper wears the armband," Iraola said in August.
"Because if something happens in the opposition box the referee has to explain to the captains what's happening, all the decisions.
"I had one season with [goalkeeper] Neto [as captain] in Bournemouth and then you have to start every game to say a different player that can act as a captain, and this is not viable.
"But I wanted him to feel like we value him. I've had enough time and we will have more time to know each other, but I had to explain also the decision about the armband to Ali because he is a keeper and, unfortunately, they are putting the rules in a way that there is a lot of disadvantages to having a keeper as a captain."
Alisson is technically Liverpool's vice-captain but will not wear the armband (Getty)
The 30-year-old Tsimikas joined Liverpool in 2020 and is the longest-serving outfield player starting for the Reds in Austria.
Iraola confirmed before the start of the season that Dominik Szoboszlai and Joe Gomez were also among his vice-captains, but Gomez is on the bench while Szoboszlai remains injured.
Tsimikas wore the armband in pre-season, taking the captaincy from Gomez after the defender was forced off with an injury in the game against Sunderland.
Liverpool XI:Alisson, Frimpong, Jacquet, Araujo, Tsimikas; Gravenberch, Nyoni; Ngumoha, Wirtz, Barcola; Koumas
Subs:Mamardashvili, Woodman, Gomez, Van Dijk, Kerkez, Mac Allister, Munoz, Chambers, McConnell, Danns, Sonni-Lambie, Lucky.
