The 44-year-old coach will reveal his decision to quit the Galician club on Friday as he prepares to take over from Gerardo Martino at Camp Nou in the summer
The 44-year-old held talks with the Catalan club at his home in Gava earlier this month and has agreed to take over from current coach Gerardo Martino to lead a new sporting project in 2014-15.
Luis Enrique played at Camp Nou between 1996 and 2004 and still has strong links at the club.
The Asturian, who previously spent five seasons at Real Madrid, has never hidden his preference for the Blaugrana and returned to coach Barca B for three years between 2008 and 2011.
He then moved to Roma, but lasted just one season at the Stadio Olimpico and was out of the game for a while until taking over at Celta last summer.
He was strongly linked with Barca after Tito Vilanova stepped down on health grounds, but was already under contract at the Galician side.
Less than a year on, however, he is now set to take over from Martino, who will announce his decision to move on at the end of the season.
Barca host Atletico Madrid in a title decider at Camp Nou on Saturday, in what will be Martino's last game as coach.