Using pulse radiolysis, rate constants have been measured for the reactions of the hydroxyalkyl radicals ĊH2OH, ĊH3CHOH, (CH3)2ĊOH, ĊH2CH2OH and ĊH2C(CH3)2OH with CuI and CuII ions in aqueous solutions. For CuII the reaction was followed by observing the rate of formation of CuI which was measured as the CuI—acrylamide or CuI—ethylene complexes. For the reaction of the α-hydroxyalkyl radicals with CuII the rate constants decrease in the order primary > secondary > tertiary and have values of the order of 108 dm3 mol–1 s–1. These results are consistent with the reaction proceeding via organocopper complexes, but these complexes have not been directly observed. The β-radicals react more slowly than the α-radicals and ethylene oxide is produced in the oxidation of ĊH2CH2OH by Cu2+. Rate constants for the reaction of the α- and β-radicals with Cu+ are estimated to be ∼ 1010 dm3 mol–1 s–1, and for the reaction of the β-radicals with the CuI—ethylene complex are estimated to be ∼5 × 107 dm3 mol–1 s–1. Organocopper intermediates in the reactions with Cu+ have been observed spectrophotometrically and absorb in the region 350–550 nm. The β-radicals oxidise CuI to CuII and are themselves reduced to the corresponding olefin. The CuI—α-radical complexes decompose to Cu+ and the radical which then reduces the Cu2+ present. Mechanisms for these reactions are proposed. Rate constants have also been obtained for the addition of the radicals (not ĊH2CH2OH) to acrylamide (∼3 × 107 dm3 mol–1 s–1) and ĊH2CH2OH to ethylene (∼2 × 106 dm3 mol–1 s–1).