PSG terminated the contract of Christophe Galtier earlier on Wednesday and have wasted little time in naming the Frenchman's successor.
Galtier was sacked for PSG's Champions League failure despite them once again winning the French Ligue 1 title.
Enrique has been tasked with putting together a squad capable of becoming a dominant force in Europe and maintaining their stronghold in France.
The 53-year-old was last in charge of Spain but left following their surprise round of 16 exit to Morocco at the 2022 FIFA World Cup in Qatar.
Enrique's last role at club level was at Barcelona, where he won nine trophies in total, including a famous treble in the 2014/2015 season.
"Paris Saint-Germain is delighted to announce that Luis Enrique has been named as its first team's new head coach, with the Spanish manager signing a two-year contract," the club wrote on their official website.
Enrique added: "I'm delighted to be joining Paris in order to enjoy a new experience.
"It's so exciting to meet new people, to live in this city, to learn a new language and, above all, to manage PSG."
Enrique also counts AS Roma and Celta Vigo among the clubs he has managed.
