The principal products formed from 1-ethoxyethyl hydroperoxide and 1,2-diphenylethyl hydroperoxide on oxidation with reagents that are presumed to generate the corresponding sec-alkylperoxy radicals (Ce(IV), tert-butoxy, and Ag2O) have been identified. The products formed when the corresponding alkoxy radicals are generated in pairs have also been identified. It is concluded that the Russell (1) concerted cyclic mechanism in which tetroxide decomposed to molecular products is not the exclusive route for the bimolecular self-reaction of sec-alkylperoxy radicals. It is suggested that there is also a second tetroxide decomposition process which yields radical products. The second process may yield "free" alkoxy radicals or it may, perhaps, yield the products of β-scission of the alkoxy radicals in a step concerted with O—O homolysis of the tetroxide. The relative importance of tetroxide decomposition to molecular and to radical products will depend on the structure of the alkyl groups, the temperature and, perhaps, the solvent.