The refugees are from Eritrea, Ethiopia, Somalia and Sudan and include a seven-month old Somali baby born in detention and 52 unaccompanied children. The Somali infant is travelling with his parents, according to the statement.
Many of the refugees had been in detention in Libya for long periods and some of them had been held for over eight months.
Nearly 4,000 refugees remain in detention in Libya, the statement said, reiterating previous calls by the UN to free all refugees and asylum-seekers being held in Libyan facilities.
"Today we have taken 98 people to safety, but this is still only a small number compared to the thousands who need such help," said Jean-Paul Cavalieri, UNHCR Chief of Mission for Libya.
"There are still some 3,600 refugees in detention centres. We urgently need to find solutions for them, as well as thousands more vulnerable refugees living in urban areas," he underlined.
With Libya continuing to suffer the consequences of ongoing conflict, such evacuations are a lifeline for the most vulnerable refugees living in detention centres and urban areas, who are in dire need of safety and protection, said the statement.
"Today's evacuation is an example of solidarity, and we thank the Italian authorities for making this possible. We hope that other countries will heed this example and provide similar, life-saving humanitarian evacuations," said Roland Schilling, UNHCR Regional Representative for Southern Europe.
Before they were freed from detention and flown to Italy, the refugees were hosted in UNHCR's Gathering and Departure Facility in Tripoli, where they were provided with food, shelter, medical assistance including psycho-social support, as well as clothes and hygiene kits.
Libya's Interior Ministry and the agency's partner LibAid helped secure the refugees' release and transfer from detention, the statement said.
UNHCR has now helped a total 1,474 vulnerable refugees to Libya this year of whom 710 were evacuated to Niger, 393 to Italy and 371 were resettled to other countries in Europe and Canada.