Water insoluble α-tocopherol films were deposited on the surface of gold, glassy carbon and platinum electrodes and their voltammetric behavior examined in aqueous solutions between pH 3 and 13. The voltammetric mechanism involved α-tocopherol being oxidized in a −2e−/−H+ process to form a phenoxonium cation, which underwent rapid reaction with water (or −OH at pH > 7) and rearrangement to form α-tocopherol quinone in a chemically irreversible process. The identity of α-tocopherol quinone was determined by reflectance-FTIR spectroscopy of the product on the glassy carbon electrode surface and from comparison of the voltammetric data obtained with a sample of the α-tocopherol quinone model compound. α-Tocopherol quinone films could be voltammetrically reduced at negative potentials to form α-tocopherol hydroquinone in a +2e−/+2H+ chemically reversible process. Experiments were also conducted by incorporating α-tocopherol into lipid (lecithin) multilayers deposited onto the electrode surfaces and the electr...