The police were carrying out their nightly patrols when a group of youngsters alerted them to the family, who were set to spent the night camped under a bridge in the Calabrian city.
The bridge was located close to the ASP, the local health authority, according to a police statement.
Officers described a "touching scene" as the young woman, in tears, told them her story.
The woman, who was in her 20's, explained to police that her husband had abandoned her and the children, who were aged three, two and a baby of just four months. She had left her native Romania and travelled to Italy to ask for help from relatives living there.
However, after a week staying with her family members, she had to leave as they were unable to look after the family.
The officers looked after the babies and checked their state of health, before trying to assist them in finding accommodation.
But even as it became clear that the local refuges and shelters were full, the kindhearted officers weren't going to give up, and accompanied the family to a hotel in the city centre where they paid for their stay out of their own pocket.
Back in August, Rome police warmed hearts around the world after cooking pasta for a lonely elderly couple. The pair had been crying so loudly that their neighbours alerted police, who cooked the pensioners a simple meal of pasta and parmesan.