The formation mechanisms of γ-ray-induced carboxyl (HOCO) and methyl radicals in CO2 + methane mixed gas hydrates, which are inclusion compounds of H2O, CO2, and methane, were investigated. The HOCO and methyl radicals were observed in CO2 + methane mixed gas hydrates by electron spin resonance (ESR) at 120 K after irradiation at 77 K. The amounts of the HOCO and methyl radicals induced in the mixed hydrates are much higher than those in pure CO2 and methane hydrates. Both radicals are synergistically formed in the mixed hydrates by efficient reactions between the guest molecules (CO2 and methane) and the active species (electron, proton, and hydroxyl radical) induced from H2O.