Gunmen travelling in two cars on Tuesday abducted Jordanian Ambassador Fawaz Aitan, the Libyan authorities said.
The Jordanian prime minister said that the envoy’s release was being negotiated.
Libya has been plagued by instability since armed groups toppled Col. Muammar Gaddafi from power in 2011.
“The Jordanian ambassador was kidnapped this morning. His convoy was attacked by a group of hooded men on board two civilian cars,” government spokesman Said Lassoued told AFP news agency.
On Sunday, Libya’s newly appointed PM Abdullah al-Thinni stepped down after what he described as a “cowardly attack” on him and his family by a militia.
Abdullah al-Thinni had been appointed as PM after his predecessor Ali Zeidan was sacked for failing to improve security.
Several kidnappings of officials in Libya in previous months have been blamed on militiamen.
They are often paid by the government, but their allegiance and who controls them remain in doubt.
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