Spanish great Andres Iniesta scored a sublime first goal for Japanese side Vissel Kobe on Saturday, helping them to a 2-1 win over J-League rivals Jubilo Iwata.
Defenders Gerard Pique and Sergi Roberto were also named new vice-captains in a statement by the La Liga champions.
The Argentina worldwide takes over from Iniesta following his move to Vissel Kobe in the J League at the end of the 2017-18 campaign.
The club confirmed: "The No.10 (Messi) who filled the role of second captain since 2015 will this season be the team's captain, a title that has shone over this past decade on the arms of other club legends like Puyol, Xavi and Iniesta".
Midfielder Sergio Busquets was named first vice-captain, followed by Pique, who has been at Barcelona since 2008.
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The five-time Ballon d'Or victor will be aiming to lift his first trophy as captain on Sunday when Ernesto Valverde's side take on Sevilla in the Spanish Supercopa.
Utility player Sergio Roberto becomes the fourth captain, taking over from Javier Mascherano, who left the club in January.
Roberto's elevation is in spite of his only being a first team regular for three seasons.
All four captains are graduates of La Masia, Barcelona's famed youth academy.