Polymer peroxides were generated onto polypropylene and polyurethane films, and polyester fibers by ozonization, UV irradiation, and plasma treatment. Their thermal and redox decompositions were studied using two assays : peroxidase and iodide. They may differ in the sensitivity to access the peroxides, depending on their localization in the polymer substrates. It was found that the generated peroxides are likely to be distributed not only on the outermost surface, but also in the subsurface of the polymer substrates. Plasma treatment provided polyurethane film with easily accessible peroxides, while UV irradiation and ozonization generated peroxides that were mostly incapable of reacting with aqueous solution of peroxidase. Redox decomposition of the peroxide groups by ferrous ions at 25 degrees C showed that less than 50% of peroxides could react with ferrous ions with a rate constant similar to that of hydrogen peroxide in aqueous solution. Thermal decomposition of the peroxides did not obey the first-order kinetics, probably due to formation of not single peroxide species with different decomposition rate constants. The lowest decomposition rate constant observed at 65 degrees C was 3 X 10(-3) min(-1), which did not depend on the polymer substrate nature and the method of peroxide generation.