The 44-year-old coach revealed 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, but refused to confirm or deny his imminent return on Friday.
"Today is a sad day," he said. "Today I am coach of Celta and I will be until the end of the season. I felt obliged to let the club know my plans, so they have time to prepare.
"There is no exclusive reason [for my departure], but I left my family behind in Barcelona and that has been hard.
"I can't confirm or deny anything. In terms of my future, there is nothing to talk about. If an interesting situation arises in future, I will communicate that."
The Asturian, who previously spent five seasons at Real Madrid as a player, 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 last July, 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.
Luis Enrique's decision to meet Barca at his home while coach of Celta and with Martino still at Camp Nou caused controversy recently, but the Galicians' president Carlos Mourinho claimed on Friday that the Asturian was free to talk to the Catalan club.
"Luis Enrique had permission to go to Barcelona that day and meet with whomever he wanted," he said. "We were in agreement."