Pozzovivo continued his preparation for his main goal in 2014, the Giro d'Italia, by racing the Giro del Trentino, where he finished second to Cadel Evans. Two days later, he was one of the main protagonists in Liege-Bastogne-Liege, a race he was participating in for the first time. He attacked with Julian Arredondo on the Cote de Roche aux Faucons, and although he was caught, he attacked again with Giampaolo Caruso on the Cote de Saint-Nicolas, and was caught with only 200 meters to go, eventually finishing 5th.