Radical cations of vitamin E compounds (α-, β-, γ- and δ-tocopherols and α-, β-, γ- and δ-tocotrienols) were for the first time successfully prepared in different solvents. Their unpaired electron distribution was solved by means of EPR and ENDOR spectroscopy and assignment of isotropic hyperfine couplings was performed. The isotropic hyperfine coupling constants calculated theoretically (UB3LYP) were comparable to those studied experimentally. Radical cations were observed to exist as an intermediate product in the formation of the neutral radical. Moreover, loosening the proton from the radical cation of α-tocopherol and from α-tocotrienol produced the neutral radical, which was detected in the ENDOR spectrum. The potency of the hydroxyl proton of the radical cation for further reactions as a measure of the biological activity of various tocopherol and tocotrienol compound is discussed.