The Barcelona legend has signed a two-year deal with the club after caretaker Abel Resino stepped down despite safeguarding its Liga status last season.
Caretaker boss Abel Resino made way despite successfully saving the Celestes from relegation last term, marking Enrique's second tenure as a professional coach following his stint in Italy with Roma.
"Luis Enrique Martinez Garcia is now the new coach of Real Club Celta following agreement between the club and individual for the next two seasons," read a statement on the club's official website.
"The former international brings an exciting attacking game, a steady outlook on the youth department and great competitiveness honed with Barcelona 'B' and Roma."
Enrique had taken a sabbatical from the sport when he walked away from the Giallorossi after an underwhelming seventh-placed finish in 2011-12.
His task to transform the fortunes of struggler Celta has been made tougher following the sale of star forward Iago Aspas, who joined Liverpool for 8 million euros earlier this month.