[2] Pessotto was given the nickname Il Professorino ("The Little Professor") by the fans, due to his glasses, his interest in philosophy and literature, and as he was able to obtain a law degree during his career.

After greatly impressing in his debut Serie A season, Pessotto moved to city rivals and European giants Juventus, in 1995, in what was a very highly regarded transfer.

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 12-year tenure with the club.

Injuries and other issues in the closing stages of his career limited his first-team opportunities to mainly being used as a substitute to Jonathan Zebina or Lilian Thuram.

[3] In total, Pessotto was capped 22 times for Italy between 1996 and 2002, under managers Arrigo Sacchi (1996), Cesare Maldini (1996–98), Dino Zoff (1998–2000) and Giovanni Trapattoni (2000–2002).

[5] He played for his country at the 1998 FIFA World Cup, where Italy were eliminated by hosts and eventual champions France on penalties in the quarter-finals, and at Euro 2000.

[9] Despite initially not being known as the most naturally talented, flashy, or technically gifted footballer, Pessotto was considered to be a promising prospect in his youth, and later made a name for himself as a correct, hard-working, reliable, tactically intelligent, efficient, and versatile utility player, with solid ball control and a good positional sense, who was able to play as an attacking full-back or wing-back, or also as a wide midfielder on either flank.

In this role, he was known for his pace, calm composure, reading of the game, and stamina, as well as his ability to chase and close down opponents, win back the ball with his tackles, and subsequently carry it up the flank, play exchanges with teammates, get forward, and deliver crosses into the area, courtesy of his distribution and ability to make attacking runs, which enabled him to cover the flank effectively.

He was also capable of playing as a central or defensive midfielder, and was even used as a centre-back on occasion, due to his consistency, awareness, and man-marking ability.

In spite of his reserved character, his sportsmanship, fair-play attitude, professionalism, discipline, elegant playing style, and gregariousness made him an important, well-liked, and respected figure in the dressing room, among both his teammates and managers.