Luigi Di Maio and interim prime minister Abdul Hamid Dbeibah, who was sworn in on Monday, discussed "cooperation and issues of common interest, foremost immigration", the premier's office said.
People traffickers have thrived amid lawlessness since the 2001 overthrow of dictator Muammar Gaddafi's regime, making the North African country a main conduit for migrants seeking to cross the Mediterranean to reach Italy and other European countries.
"Italy and Libya are united by important geo-strategic interests," Di Maio said in a statement on social media.
"In addition to the issue of migration flows, I reiterated that it is essential for us to relaunch economic cooperation between our countries."
Dbeibah also met with Claudio Descalzi, chief executive of Italian energy giant Eni, discussing "ways to reinforce cooperation in the area of renewable energy", Dbeibah's office said.
The prime minister called on the group, which has operated in the oil-rich country for decades, to also "invest in the areas of health, education and electricity".
He said electricity was an "absolute priority for Libya", which suffers from chronic power cuts.
Eni said Descalzi confirmed the company's "full commitment regarding operational activities and projects in the country, focusing on natural gas, a strategic resource for Eni in its energy transition and for Libya".
"The company will continue to play a major role in gas production thanks to the new relevant offshore development projects," Eni said.
Di Maio is the first European official to visit Libya since the formation of its new interim government.
President Kais Saied visited from neighbouring Tunisia on Wednesday, in the first head-of-state visit from Tunis since 2012.
Dbeibah's swearing-in came after parliament last week approved his cabinet, in a move hailed by key leaders and foreign powers as "historic".
A United Nations-supervised process is working to unite Libya, building on an October ceasefire between rival administrations in the country's east and west.
But the new executive faces daunting challenges to unify institutions, end a decade of fighting marked by international interference and prepare for elections on December 24.
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