The irradiation consequences on styrene-isoprene-styrene (SIS)/poly(ε-caprolactone) (PCL) blends are discussed starting from the oxidation initiation. Three characterization methods: chemiluminescence, differential scanning calorimetry and FTIR spectroscopy are applied. The differences that exist between the two components are revealed, when the oxidation rates of the inspected formulas depend on the blending proportion and the degradation conditions. The relevant activation energies characterizing the oxidation strength as well as the kinetic parameters of degradation during the accelerated damaging of blended polymers are related to the inhibition protection of PCL on the faster oxidation of SIS. The interaction between mixed components is revealed by the structural modifications simultaneously accompanied by the competition of formation and decay of radicals.