The 63-year-old, who coached Spain from 1992-98, replaces Abdelhafidh al-Rabich who stepped down after Libya were eliminated from the 2014 FIFA World Cup™. Clemente will attempt to guide the side to the 2015 CAF Africa Cup of Nations to be held in Morocco.
Clemente, who also coached Serbia and Cameroon, called for the support of the clubs, the fans and the press in order to make his task easier to achieve.
As well as his international experience, Clemente has coached Spanish club sides including Athletic Bilbao and Atletico Madrid and was also briefly in charge of Sporting Gijon last year in the top flight. Libya will host the CAF Africa Cup of Nations in 2017.