A product analysis and kinetic study of the one-electron oxidation of a number of 1-arylpropanols, 1,2-diarylethanols, and some of their methyl ethers by potassium 12-tungstocobaltate(III) (abbreviated as Co(III)W) in aqueous acetic acid was carried out and complemented by pulse radiolysis experiments. The oxidations occur via radical cations which undergo side-chain fragmentation involving the C-alpha-H and/or C-alpha-C-beta bond. With 1-(4-methoxyphenyl)-2-methoxypropane (1), only deprotonation of the radical cation is observed. In contrast, removing the ring methoxy group leads to exclusive C-C bond cleavage in the radical cation. Replacing the side-chain beta-OMe by beta-OH, the radical cation undergoes both C-C and C-H bond cleavage, with both pathways being base catalyzed.