Messi's 21-year stay at Barcelona came to an end after the club failed to reduce their wages to be able to sign a new deal with the 34-year-old, whose contract expired in June.
And to replace his position as the club captain, Barcelona have appointed Sergio Busquets, followed by Gerard Pique, Sergio Roberto and Jordi Alba.
Busquets, Pique and Sergi Roberto were among the vice-captains in previous seasons, with Alba being named for the first time.
Busquets had his debut as Barcelona captain in Sunday's Joan Gamper Trophy fixture against Juventus.
The exit of Messi saw Busquets bidding an emotional farewell to his former teammate and captain.
"You arrived as a child and you are the best player in history, having made this club grow to the height that it deserves and making history individually and collectively.
"I can always say that I played and shared many moments with you, most of them very good and I was lucky to grow up and enjoy 13 seasons with you.
"Beyond all this I remain with the person and the friendship that we made, I will miss you a lot.
"I can only wish you and your family the best because you deserve it, you will be missed."
The new captains for Barcelona all came through the club's youth academy known as La Masia.
The recent figures to have worn the armband before Lionel Messi are Carles Puyol, Xavi Hernandez and Andres Iniesta.
