Decomposition of tetralyl and cyclohexenyl hydroperoxides catalyzed by complex copper salts was studied in chlorobenzene and ethanol. It was shown that alcohol significantly accelerated the thermal decomposition in the absence of the catalyst. In comparison with chlorobenzene, the catalytic decomposition of hydroperoxides in alcohol is characterized by higher initial rates of the reaction, the absence or weak deactivation of the catalyst under the same experimental conditions and, as a consequence, a significantly higher catalysis factor. The results are interpreted in terms of the formation of intermolecular complexes with hydrogen bonds between the substrate, intermediate radicals, and alcohol.