The 37 Syrian families, who include some Chaldean Christians and were chosen because of vulnerability or illness, join more than 90 other Syrian families already flown to Rome under the same programme.
They had been living in a refugee camp in Lebanon and were flown in from Beirut.
Sant'Egidio's aim is to find homes for 1,000 refugees in Italy over two years.
"Through this experience we are saying to our friends at the European Union that Europe cannot be a frightened fortress," the charity's founder Andrea Riccardi told Reuters. "Europe has its responsibilities to the world if it wants to continue to call itself Europe, because a Europe with walls is no longer Europe."
Khalid Chaouki, a deputy of the Democratic Party, wrote for the Huffington Post: "Humanitarian corridors are a message of hope for Europe." He said the refugees were people in particularly "vulnerable" states and were mostly single women with children, the elderly, sick and disabled and victims of persecution and torture.
He said this was the third time a "corridor" had been activated and was made possible thanks to Italy's ministry of foreign affairs, Sant'Egidio, Italy's Federation of Evangelical Churches and the Waldensian Church.
The programme means these people will avoid risking their lives in the Mediterranean or becoming victims of human traffickers, he added.
"They will go to courses to learn Italian and start a new life, away from the bombs and the Syrian violence," he wrote.
Vita reported: "Humanitarian corridors are the synthesis of legality and security. We are faced with a model that works for European institutions."