The measurements of the UV-vis absorption spectra of α-, β-, γ-, and δ-tocopheroxyl (α-, β-, γ-, and δ-Toc•) radicals were performed by reacting aroxyl (ArO•) radical with α-, β-, γ-, and δ-tocopherol (α-, β-, γ-, and δ-TocH), respectively, in acetonitrile solution including three kinds of alkali and alkaline earth metal salts (LiClO4, NaClO4, and Mg(ClO4)2) (MX or MX2), using stopped-flow spectrophotometry. The maximum wavelengths (λmax) of the absorption spectra of the α-, β-, γ-, and δ-Toc • located at 425-428 nm without metal salts increased with increasing concentrations of metal salts (0-0.500 M) in acetonitrile and approached some constant values, suggesting (Toc•· · ·•M+ (or M2+)) complex formations. Similarly, the values of the apparent molar extinction coefficient ( max) increased drastically with increasing concentrations of metal salts in acetonitrile and approached some constant values. The result suggests that the formations of Toc• dimers were suppressed by the metal ion complex formations of Toc• radicals. The stability constants (K) were determined for Li+, Na+, and Mg2+ complexes of α-, β-, γ-, and δ-Toc•. The K values increased in the order of NaClO4 < LiClO4 < Mg(ClO4)2, being independent of the kinds of Toc • radicals. Furthermore, the K values increased in the order of δ- < γ- < β- < α-Toc• radicals for each metal salt. The alkali and alkaline earth metal salts having a smaller ionic radius of the cation and a larger charge of the cation gave a larger shift of the λmax value, a larger εmax value, and a larger K value. The result of the DFT molecular orbital calculations indicated that the α-, β-, γ-, and δ-Toc• radicals were stabilized by the (1:1) complex formation with metal cations (Li +, Na+, and Mg2+). Stabilization energy (E S) due to the complex formation increased in the order of Na + < Li+ < Mg2+ complexes, being independent of the kinds of Toc• radicals. The calculated result also indicated that the metal cations coordinate to the O atom at the sixth position of α-, β-, γ-, and δ-Toc• radicals. © 2012 American Chemical Society.