Born in Naples to an Italian father, Salvatore, and an Australian mother, Carolyn, he moved to Australia at the age of three, coming back to Italy at six. Rosolino declared about his beginnings as a swimmer:
I learned to float by sheer chance at the age of 4. Instead of the common arm floating bands, they made me swim with a headboard. Unfortunately it had a hole, and by the time I finally got out of the small and deep pool, the headboard had drowned... The first real swimming course I took was when I was 6 years old, and after that, lesson by lesson, I got to the pre-competition level. I always had a hard life, even though I was physically well-built, I always had to fight to become number 1, and even though I won a lot of races, I remember every race with emotion: the first regional championships, the national ones, the Young Europeans, and of course all the stomach aches I had.
Rosolino represented Italy in all of the four editions of the Olympic Games since 1996. At the 2000 Olympic GamesinSydney, he became the second Olympic champion ever in the history of Italian swimming as he won the gold medal in the 200 m individual medley (1:58.98, then Olympic and national record). He won two more medals: a silver medal in the 400 m freestyle setting the current European record (3:43.40) behind Ian Thorpe, and a bronze medal in the 200 m freestyle (1:46.65) behind Pieter van den Hoogenband and Ian Thorpe. At the 2004 Olympic GamesinAthens, Rosolino won a bronze medal with the Italian team in the 4×200 m freestyle relay.