"For the first time a humanitarian corridor has been opened from Libya to Europe. It's a start," Minniti said, adding: "Today is a historic day."
Those evacuated came from Eritrea, Ethiopia, Somalia and Yemen. They comprised families, single mothers, unaccompanied children and handicapped people, who were flown on a military jet.
Vincent Cochetel, the UNHCR's special envoy for the central Mediterranean, said: "For the first time, we have been able to evacuate extremely vulnerable refugees from Libya directly to Italy. Many of those evacuated spoke of great suffering and were kept prisoners by traffickers in inhuman conditions."
Libya has long been a transit hub for migrants seeking a better life in Europe, but people smugglers have stepped up their lucrative business in the chaos since the 2011 revolution.
Libyan authorities have come under fire over migrant abuses since the airing last month of CNN footage of a slave market in the North African country.
The United Nations has urgently appealed for countries to take in 1,300 "extremely vulnerable" refugees stranded in Libya.