MORE: Vincenzo Nibali wins Tour de France | Tour de France Stage 21 Photos
Nibali became only the sixth man to win each of the three Grand Tour races when he crossed the line on the Champs-Elysees in Paris, confirming a victory that had already been all but secured prior to Sunday's final stage.
After winning the Vuelta a Espana in 2010 and the Giro d'Italia last year, Nibali joins an exclusive club that features Jacques Anquetil, Felice Gimondi, Eddy Merckx, Bernard Hinault and Alberto Contador.
The Italian's winning margin of seven minutes and 37 seconds was the largest since Jan Ullrich's success 14 years ago.
Astana rider Nibali is also the first Italian to win the Tour since Marco Pantani achieved the feat in 1998.
And the 29-year-old could not hide his delight after etching his name into cycling's history books.
"I almost can't breathe, it's really incredible, fantastic, fabulous, unbelievable," Nibali said.
"I'm so excited I cannot event talk. I was sometimes a little afraid, but the held was fine and I was in good physical condition."
Nibali also praised the way cycling has tackled the problem of doping in the sport - something he feels has been further evidenced by his win.
"My victory is a good sign for the fight against doping? Yes, but not just mine," he added.
"In recent years, there have been others [winners who were] important and clean.
"Cycling has changed and we can be proud."