After experiencing appalling living conditions at camps in the north African country, the refugees were taken to Niger on 11 November by the UN High Commissioner for Refugees (UNHCR), where they have been looked after.
The 25 Eritreans, Ethiopians and Sudanese -- including 15 women and four children -- should reach France "at the latest in January," the interior ministry said.
Libya has long been a major transit hub for migrants trying to reach Europe, and many of them have fallen prey to serious abuse at the hands of traffickers and others.
US television network CNN aired footage last week of an apparent live auction where black men are presented to buyers as potential farmhands and sold off for as little as 340 euros.
And the European Union's policy of helping Libyan authorities intercept migrants crossing the Mediterranean and returning them to "horrific" detention has been branded "inhuman" by UN human rights chief Zeid Ra'ad Al Hussein.
Pascal Brice, the director general of OFPRA (French Office for the Protection of Refugees and Stateless Persons) told the news agency AFP that France will take in the migrants following a visit to Niger's capital Niamey.
He said the migrants -- who were selected because they need protection -- will be given refugee status "very quickly" when they arrive in France.
"It is above all a way of saving people who have come out of a hell, with torture, rape and abduction of children," Brice said, adding the refugees were "almost all victims of sexual violence".
"The challenge now is that other countries, Europeans, Americans, Canadians, join this process," said Brice.
A further 47 refugees who were already living in Niger will also be taken in by France.
Alessandra Morelli, head of UNHCR in Niamey, said "we have done miracles" following the evacuation.
Although the figure of 25 refugees is tiny when compared to the 44,000 registered by UNHCR in Libya, Morelli said "we are convinced that there will be other operations".