Rome said it would grant asylum to Asia Bibi following a request for assistance from her husband, Ashiq Masih.
Italian deputy prime minister Matteo Salvini said: "I want women and children whose lives are at risk to be able to have a secure future, in our country or in other Western countries.
"So, I will do everything humanly possible to guarantee that [for Ms Bibi]."
Mr Masih had previously urged the UK, US and Canada to give his wife refuge.
It is yet to be confirmed where Asia Bibi will travel to once she is released.
A decision by Supreme Court judges in Islamabad to free the 47 year old from a charge of blasphemy prompted protests in major cities last week.
Hardline Islamists held banners demanding her public execution and threatened to continue blocking major roads until the ruling was reviewed.
A deal struck by the government of prime minister Imran Khan to avert further disruption saw an agreement to initiate exit-control list proceedings against Asia Bibi, meaning she could be stopped from leaving the country.
Prior to her acquittal, Asia Bibi had been on death row for eight years after being convicted of insulting Islam's prophet Mohammad. She always denied any wrongdoing.
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