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Abstract The kinetics of oxidation of α,β-unsaturated compounds by platinum(IV) in the presence of alkali {[OH−]= (1–9) × 10−3 mol dm−3} have been investigated over the 303–318 K temperature range . The rate of the reaction is dependent on the first power of the concentrations of substrates, oxidant, and alkali. The rate constant increases with an increase in ionic strength and also with increasing dielectric constant of the medium. The oxidation rates follow the order: –CN > –CONH2 > –COO−. The values of the third order rate constant (k3) for the oxidation of acrylonitrile, acrylamide and acrylate are 1.24, 0.826 and 0.628 mol−2 dm6 s−1 respectively, at 303 K. The oxidations of the substrates by PtCl5(OH)2− take place by an inner-sphere mechanism. Platinum(IV) is reduced to platinum(II) by the substrates in a one-step two-electron transfer process to give reaction products. The major reaction product, HCHO, is identified from the reaction mixture using i.r. spectrometry, n.m.r. and C, H, N analysis. A tentative reaction mechanism, leading to the formation of products, has been suggested. The activation parameters of the reaction have been evaluated.