The 44-year-old Spaniard has signed a two-year contract with an option for a third having earlier this month left Sevilla, where he won three successive Europa Leagues.
European success was the one thing that eluded Blanc during his time in the French capital, with three successive Ligue 1 titles among a haul of 11 trophies in total before leaving the role by mutual agreement on Monday.
Emery told his new club’s official website, psg.fr: “It is with much pride that I have accepted the mission of coaching Paris St Germain.
“I know there is an immense passion for Paris Saint-Germain and I will give my all to bring their millions of fans great moments of joy.”
Emery began his career with Lorca, where he ended his playing career, and guided them to the Spanish second tier for the first time in their history. He moved on to Almeria, lifting them to the Primera Division and earning a move to Valencia.
His debut season saw Los Che finish sixth and qualify for the Europa League, before back-to-back third-place finishes and Champions League qualifications. A brief spell at Spartak Moscow then preceded his triumphant three-and-a-half years with Sevilla.
PSG president Nasser Al-Khelaifi said: “I am very happy to welcome Unai Emery as the new coach of Paris St Germain. Unai will bring to the club all his experience, his passion and his great qualities in management and as a man.
“He has a talent for getting the best out of a team. I am conviced our fans will enjoy the spectacular style of football the team will play under Unai’s management.”