The Gunners have been searching for new recruits for much of the summer, with competition for Polish pair Wojciech Szczesny and Lukasz Fabianski one of their top priorities.
Viviano was a regular for Fiorentina last season, playing 32 times during a loan spell with La Viola as Vincenzo Montella's side finished fourth in Serie A.
Despite being a regular starter, Fiorentina decided not to make the loan deal permanent, forcing the Azzurri keeper to rejoin Palermo, who were relegated to Serie B last season.
Palermo are looking to get high earners off the wage bill and have agreed to sanction a loan move for Viviano to join the Gunners.
Viviano will now travel to London tonight to talk personal terms ahead of a medical at London Colney, according to Sky Sport Italia.
The 27-year-old has played 10 times for his country, regularly standing in for Gianluigi Buffon since making his debut in 2010.