Vitamin E is a generic term for all tocopherol and tocotrienol derivatives. The most abundant and active form of vitamin E isoforms in vivo is alpha-tocopherol, but recently the roles of other forms of vitamin E have received renewed attention. In this review, we summarize the differences among alpha-, beta-, gamma-, delta-tocopherols and tocotrienols specifically regarding the following points; (i) their radical-scavenging efficacies and chemical reactivity with metal ions in solution, (ii) their physical effects at the liposomal membrane interior, and (iii) their protective effects against cell toxicity. Moreover, the physiological significance and future prospects for using vitamin E, especially tocotrienols, for the prevention and treatment of disease are discussed.