Exchanges of fire with heavy weapons forced the closure of Tripoli airport, as foreign ministers from the North African nation's neighbours were to meet later in Tunisia to consider how to aid chaos-riddled Libya.
A health ministry spokesman, speaking on condition of anonymity, said at least six people were killed and 25 wounded in the clashes.
It was not immediately known if civilians were among the casualties.
The assault on the Zintan group by rival Islamist militants also came after the UN pulled staff from Libya citing security reasons, and as the United States warned of further escalation.
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Loud explosions and heavy gunfire were heard in the city centre, 25 kilometres away, AFP correspondents reported.
An airport source said Zintan fighters pushed back the assailants but that clashes continued to rage around the facility, as locals reported seeing tanks deploy and smoke billowing.
Authorities closed the airport for at least three days from today after initially halting flights.
The former rebel Zintan militia helped topple strongman Muammer Gaddafi in the 2011 NATO-backed uprising, and is now well established in Tripoli, controlling the airport and military sites.
Today's attack was claimed by the Operations Cell of Libyan Revolutionaries, a coalition of Islamist militias seen as the armed wing of Islamists within the General National Congress or parliament.
"The revolutionary forces arrive within the perimeter of Tripoli airport and clash with armed groups inside," it said on its Facebook page.
The fighting comes weeks after a contested June 25 general election to replace the Islamist-dominated GNC, which has been mired in controversy and accused of hogging power.