The former flag carrier is set to be put in administration under government-appointed commissioners after the agreement between management and unions, which featured redundancies and pay cuts, was voted against by Alitalia staff.
"I said it before and I’ll say it again - the conditions do not exist to nationalise Alitalia," Gentiloni said.
"Nevertheless, the government feels committed to defending workers, users, taxpayers and citizens so that the company's assets and resources are not wasted.
“We'll continue to work, although the outcome of the employees’ votes makes the challenge even more difficult."
Gentiloni added that he was disappointed Alitalia staff had rejected the plan and admitted he was worried about the company's future.
"I cannot silence the concern about what is happening to Alitalia," he said.
"It is necessary to be on the market to compete. I am disappointed that the opportunity of an agreement between the company and the unions was not accepted."
Labour Minister Giuliano Poletti said commissioners will explore the company’s future prospects and the possibility that new investors could take over the struggling airline.
Industry Minister Carlo Calenda said that Alitalia is set to receive a bridge loan of up to 400 million euros to keep it alive in the coming months.
"The new commissioner must ensure the company's continuity and then find a buyer for Alitalia who knows how to manage it," Calenda said.
"The only thing will be a bridge loan from the State of around 300, 400 million euros to ensure six months of administration."
When asked about reports that Lufthansa – Germany’s largest airline – had expressed interest in Alitalia, Calenda said it would be exciting to explore that avenue.
A European Commission spokesperson said on Wednesday that the EU executive was in “constructive contact” with Italy regarding Alitalia.