Pozzovivo was involved in the collision while training near Cosenza in southern Italy. The 36-year-old was taken to a local hospital and remains in intensive care.
A climbing specialist Pozzovivo helped teammate Vincenzo Nibali to a second-place finish in this year's Giro Italia.
He had been training for the Vuelta a España which starts on 24 August but will now miss the race with his team confirming "multiple bone fractures requiring surgery" in a press release.