Gerardo Martino parted company with the Catalan club at the end of a season that saw Barca miss out to Atletico Madrid for the Primera Liga title after they drew with them on the final day of the season.
Enrique left Celta Vigo after guiding them to a ninth-place finish in the Spanish league this season and has now been given the opportunity to impress on a bigger stage.
"The FC Barcelona board of directors have confirmed Luis Enrique Martineza as the new first-team coach, following a proposal from sporting director Andoni Zubizarreta," the club said in a statement on their official website.
"Luis Enrique, 44, will sign a two-year deal."
Enrique played for Barcelona from 1996-2004, moving to the Nou Camp following a five-year spell at rivals Real Madrid.
He cut his teeth in management with Barcelona B, before moving on to Roma and then Celta.