Flame-retardant ethylene propylene diene copolymer (FR-EPDM) and silicone rubber (SiR) were aged by heat with or without concurrent irradiation of gamma rays. For these samples, chemiluminescence (CL) and infrared absorption spectra were measured. Although the CL intensity decreases with an increase in total dose of gamma rays both in FR-EPDM and SiR, this negative dose-dependence is weaker in FR-EPDM than in SiR. This is reasonable, since CL appears when a substance is oxidized. Namely, the CL intensity becomes weak if the sample was already oxidized. While FR-EPDM is an organic polymer that can be oxidized easily, SiR is an inorganic polymer with siloxane bonds. Moreover, carbonyl groups appear when FR-EPDM is degraded, while SiR forms mainly a crosslinked structure by bridging two silicons by one oxygen when it is irradiated by gamma rays. Such differences in degradation mechanism between two insulating polymers are reflected on their CL properties.