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Messi was appointed the Spanish club's captain in 2018 after Barcelona legend Andres Iniesta left for Japanese side Vissel Kobe.
However, the six-time Ballon d'Or winner was unable to commit his long-term future to Barcelona due to La Liga's financial rules.
Messi, whose Barcelona deal expired at the end of June, made his emotional exit from the Camp Nou and completed a stunning free transfer move to Paris Saint-Germain.
Barcelona confirmed in an official statement that Busquets would become the club's first-team captain with Messi's departure.
The La Liga club added that Busquets will have a trio of La Masia alumni as part of Barcelona's four-man captain list.
Gerard Pique, who took a hefty pay cut to ensure Barcelona could register the likes of Eric Garcia and Memphis Depay, has been promoted from third to second captain.
Sergi Roberto has also climbed up the ranks to become Barcelona's third-choice captain, while Jordi Alba is a new addition to the quartet of captains.
Busquets, a La Masia alumnus, has spent his entire senior playing career at Barcelona and spent three seasons as the club's second captain.
The 33-year-old Spanish midfielder was previously Barcelona's third captain from 2015 and fourth-choice skipper the season before.
Barcelona manager Ronald Koeman insisted that they "have to live in the present [and] not the past" after Messi's exit.
Speaking at his pre-match press conference on Saturday, he said: "It's painful for all the Barcelona fans, for everything Messi has done.
"But we mustn't live in the past either. They are things of the past, people change teams. I'm excited, I hope we have the same enthusiasm as the Barcelona fans. We have to live in the present, not the past."
Barcelona will begin their La Liga campaign on Sunday when they host Real Sociedad at the Camp Nou.
Featured Image Credit: PA
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