Virgil van Djik will remain as club captain - in what could be his final campaign at Anfield - but Andy Robertson's summer exit means a change in the wider captaincy group.
Iraola has confirmed Alisson Becker, Joe Gomez and Dominik Szoboszlai will act deputies to Van Dijk, and cover games in which the Dutchman does not feature.
However, Iraola also admitted practicality - and new Premier League rules - mean Alisson will not wear the armband in the months ahead.
"I explained to Alisson that it’s not possible that he wears the armband because with the new rules, I think there's a big limitation if a ’keeper wears the armband.
“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 Neto in Bournemouth and then you have to start every game to say a different player that can act as a captain, it's not viable.
“I wanted him to feel that we value him. I’ve had enough time, and we will have more time to know each other, but I had to explain the decision about the armband to Ali because he's a ’keeper and, unfortunately, they're putting the rules in a way that there's a lot of disadvantages to having a ’keeper as a captain."