Between 1986 and 1991, he played with Fiorentina, collecting 122 appearances and 10 goals in Serie A over five seasons. Although he was initially acquired as a winger in 1986, the club's new Brazilian manager at the time, Sebastião Lazaroni decided to deploy him as an attacking full-back or wing-back, in the mould of offensive, Brazilian attacking fullbacks, such as Djalma Santos, due to Di Chiara's pace, technical ability, and his offensive style of play. During his time at the club, he reached the 1990 UEFA Cup Final.