Rossi was ten when he first started canoeing but he made an inauspicious start, coming last in every competition he took part in. However he became one of the greatest canoers in his country’s history.

Competing in five Summer Olympics, he won five medals which included three golds (K-1 500 m: 1996, K-2 1000 m: 1996, 2000), one silver (K-2 1000 m: 2004), and one bronze (K-2 500 m: 1992).

Rossi has also been successful at the ICF Canoe Sprint World Championships with seven medals. This includes three golds (K-2 1000 m: 1995, 1997, 1998), three silvers (K-2 1000 m: 1993, 1994; K-4 200 m: 1998), and one bronze (K-1 500 m: 1997). 

He was the Italian flag bearer at the opening ceremony of the 2008 Summer Olympics in Beijing.