BBC Wales has been told the retired player and Kate Weaver-Gibbs were involved in the incident involving a motorbike last week.
There are no further details available about the accident. The Foreign Office has been asked to comment.
Reports in Italian media suggest only Ms Weaver-Gibbs has been injured.
Ms Weaver-Gibbs, who is in her early 30s, is a beauty and travel writer who is originally from south Wales.
In a magazine article published after their wedding, she said they met at the Pelican pub in Ogmore-by-Sea, in Vale of Glamorgan, after she finished studying at Bristol University.
The couple were married in 2014 in Cape Town, South Africa.
They moved in 2009 to Aspen, Colorado, and the following year to South Africa, from where Scott Gibbs did media work.
Mr Gibbs, who is now aged 45, retired from rugby in 2004, having played 53 Tests for Wales, and on three tours with the British and Irish Lions.
He also played rugby league for Wales and for St Helens, winning the Challenge Cup.
He made his Wales union debut in 1991, with probably his most famous moment the last-minute try against England in 1999 which helped his country to a 32-31 win.
For the Lions he was named Man of the Series in the winning 1997 tour in South Africa.
Former Wales rugby international Scott Gibbs and his wife are understood to have been involved in a road accident in Italy.