"We have reached an agreement in principle for Clemente to begin work at the head of our national team starting in October," LFF president Anwar Altashani was quoted as saying by the website of Spanish sports daily AS.
The federation released a picture on Monday of Clemente arriving at Tripoli airport but made no statement.
It will be the fourth national team post for the 63-year-old Clemente, who coached Spain between 1992 and 1998, Serbia (2006-2007) and Cameroon for just over a year (2010-2011).
He has also been manager of several Spanish clubs including Athletic Bilbao, Atletico Madrid and was briefly in charge of Sporting Gijon last year in the top flight.
Clemente replaces Abul Hafidh Erbeesh, who left the post after Libya were eliminated from World Cup qualifying this month. Libya are hosts for the 2017 African Nations Cup finals.