In this study, the physicochemical properties and bioactive compounds of olive oils from cultivars “Roggianella”, “Sinopolese” and “Ottobratica”, grown in the province of Reggio Calabria (Italy) have been evaluated. Polyphenols are a large family of compounds found in fruits and vegetables, which exhibit strong antioxidant activity by scavenging different families of Reactive Oxygen Species (ROS). Dialdehydic form decarboxymethyl oleuropein aglycon, hydroxytyrosol acetate, dialdehydic form oleuropein aglycon, pinoresinol, 1-acetoxypinoresinol, tyrosol and vanillic acid were the main phenolic compounds in all samples analyzed. Pinoresinol was the most abundant compound in the lignin fraction. In all oil samples analyzed the highest antioxidant capacity was attributed to Roggianella oil (36.85% I of DPPH and 4.07% I of ABTS) compared to Ottobratica (27.37% I of DPPH and 2.52% I of ABTS) and Sinopolese (18.33% I of DPPH and 1.72% I of ABTS). The main characteristics of the Roggianella cultivar were a very high concentration of total phenols (530 mg/kg of gallic acid) and α-tocopherol (211 mg/kg).