Oxidation of α-diols, namely ethylene glycol, 1,2-propanediol, and 1,2-butanediol, by [Ag(HIO₆)₂]⁵⁻ is kinetically first-order with respect to the Ag(III) complex. The dependence of observed first-order rate constants k _obs on [α-diol] can generally be expressed by: k _obs = k _x[α-diol] + k _y[α-diol]². Our experimental results demonstrate that the different rate laws derived in the oxidation reactions of ethylene glycol (J. H. Shan et al. Chin. J. Chem. 24:478, 2006) and 1,2-butanediol (J. H. Shan et al. Transition Met. Chem. 30:651, 2005) by the Ag(III) complex are probably not correct. In turn, the reaction mechanisms based on these rate laws should probably be treated with caution.