After joining Juventus in 1995, he instantly became a key part of the first team and help Juventus form what was considered as the best defence in the world at this time, and teams strongly regretted ever going down a goal to the club, as they knew how hard it would be to score one back for themselves. Pessotto formed impressive defensive partnerships with the likes of Ciro Ferrara, Moreno Torricelli, Paolo Montero, Mark Iuliano, Lilian Thuram, Alessandro Birindelli, Igor Tudor, Gianluca Zambrotta, Nicola Legrottaglie, Fabio Cannavaro, Jonathan Zebina, and Giorgio Chiellini during his lengthy 12-year tenure with the club. He was one of many experienced players who had been at Juventus for a lengthy period of time. Injuries and other issues in the closing stages of his career limited his first-team opportunities to mainly being used a substitute to Jonathan Zebina or Lilian Thuram. Pessotto retired at the end of the 2005–2006 Serie A season, after back to back Scudetti. With Juventus he managed well over 250 total appearances scoring 2 league goals in the process. Among his achievements as a Juventus player, Pessotto won the UEFA Champions League in 1996, playing in 4 Champions League Finals, the UEFA Super Cup in 1996, the Intercontinental Cup in 1996, 1 UEFA Intertoto Cup in 2000, 4 Scudetti (1997, 1998, 2002, 2003) 4 Supercoppa Italiana (1997, 1998, 2002, 2003), and 1 Coppa Italia in 1995.