The 36-year-old climber was in the mix and was part of the main group of favourites but went down in a crash just ahead of the penultimate time climb of the Mur de Huy. The crash also brought down Adam Yates (Mitchelton-Scott) and Roman Kreuziger (Dimension Data).
Yates and Kreuziger got back on their bikes but neither would go on to finish the race. Pozzovivo stayed on the ground before being transported by ambulance to Huy hospital.
"Unfortunately we had again bad luck with the crash of Bole and in particular Pozzovivo”, said Bahrain Merida Sports Director Rik Verbrugghe.
The small Italian climber has been a victim of a number of crashes, including a particularly dramatic one at the 2015 Giro d'Italia which also saw the Grand Tour rider taken away by ambulance.
He was assessed and found to have no skull or vertebral fractures from his Fleche crash, though it was confirmed that he suffered facial trauma and concussion as well as multiple abrasions on his shoulder, elbow, hip, knee and face.
“Pozzovivo will join us at the team hotel and then we will evaluate his condition ahead of the Liège,” said Verbrugghe, not ruling Pozzovivo out despite his extensive injuries.
Mitchelton-Scott had their own issues with crashes during the race, with star rider Adam Yates and most of the rest of the squad coming down during the race.
“Six out of seven riders were involved in crashes, some of them multiple," said Michelton-Scott team director Matt White. "Lucky for us is that nobody was seriously injured but obviously Adam Yates going down with Nick Schultz and four or five others coming in with one lap to go, that was our day done.
“By the looks of it everybody looks to be ok for Sunday (at Liege-Bastogne-Liege).”
SBS will broadcast Liege-Bastogne-Liege live, with coverage beginning on Sunday 28 April at 10pm AEST on SBS VICELAND and streaming online at the Cycling Central website and via the SBS OnDemand App.