α-Tocopheryl succinate (TS) is a succinic acid ester of a well-known natural antioxidant α-tocopherol (α-T). Physicochemical characteristics of TS are entirely different from the original compound α-T. TS becomes vesicles via forming a lamella structure. Furthermore, although the antioxidative activity of α-T is lacked by esterification of phenolic hydroxyl (OH) moiety with succinate, TS has versatile biological functions, such as inhibition of cholinesterase activity, inhibition of nuclear factor-kappa B (NF-κB) activation, enhancement of lipopolysaccharide-induced nitric oxide production, and anticancer effect. Especially, we expect TS as a novel anticancer agent. TS nanovesicle shows significant anticancer activity in vitro and in vivo. Nicotinamide adenine dinucleotide phosphate (NADPH) oxidase produces superoxide which mediates the anticancer activity of TS. Moreover, it suggests that TS activates protein kinase C via direct interaction. Based on the analysis of structure and activity relationship, it ensures that succinate moiety of TS plays a vital role in anticancer activity. This review introduces the detail and mechanism of versatile biological functions of TS.