Mohamed al-Megaryef "will on Tuesday evening submit his resignation before members of the General National Congress," the national assembly, one of his advisers told AFP on condition of anonymity.
"The members of the General National Congress will elect a new president in the coming days," the adviser said, but without elaborating on the reasons for Megaryef's planned resignation.
Megaryef was Libya's ambassador to India in the 1980s before he defected and joined the opposition in exile.
On May 5, the national assembly passed a controversial law banning officials who served under Kadhafi between September 1, 1969 and the fall of his regime in October 2011 from holding any political role.
The law -- which comes into force on June 5 -- was adopted under pressure from armed groups demanding the ouster of former regime officials from current political office.
Megaryef was elected to head the GNC last August following Libya's first post-uprising elections the previous month.
Megaryef spent 31 years in exile, including 20 years as a political refugee in the United States, and along with other dissidents he founded an opposition group that had tried to overthrow Kadhafi.
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