Six monocultivar virgin olive oils (VOOs) produced from five autochthonous (Buža, Buža Puntoža, Istarska Bjelica, Porečka Rosulja, and Rosinjola) and one referent cultivar (Leccino), were investigated. The mass fractions of orthodiphenols (ORT) and tocopherols (TOC) were analysed by VIS spectroscopy and HPLC. The radical-scavenging capacity was evaluated by electron spin resonance spectroscopy (ESR) using galvinoxyl free radical and the DPPH test. Results revealed a high level of total TOC in VOOs of Buža Puntoža (243 mg kg−1) and Porečka Rosulja (325 mg kg−1). VOOs contained in 100 g from 79% (Istarska Bjelica) to 261% (Porečka Rosulja) of recommended daily allowance of α-tocopherol. The mass fraction of ORT in Istarska Bjelica and Rosinjola was >250 mg kg−1 (on average 30–40% higher in comparison to other studied cultivars). Istarska Bjelica and Porečka Rosulja showed the highest antioxidant capacity in both methods of measurement. The highest capacity to inhibit protein carbonylation (PC) in response to oxidative stress (54–56%) was displayed by Buža Puntoža, Leccino, and Buža. High level of positive linear correlation between ORT mass fraction and radical-scavenging capacity measured by DPPH test (r=0.768), as well as strong negative correlation between PC inhibition and mass fraction of ORT (r= −0.697), were observed.