Silicone rubber is widely used in radiation environments, such as the nuclear industry and aerospace, due to its excellent properties. However, irradiation can cause performance degradation. This study proposes the introduction of coumarin-based profluorescent nitroxide radicals (P_C343) into silicone rubber to achieve both radiation aging protection and sensitive monitoring. P_C343 was uniformly introduced into silicone rubber (SR-P) via a swelling method. Electron paramagnetic resonance spectroscopy confirmed that P_C343 reacts with radiation-generated free radicals in silicone rubber, demonstrating free radical scavenging ability. Gas-phase infrared spectroscopy analysis showed that P_C343 could reduce the production of alkane gases (the alkane yield of SR-P irradiated at a dose of 1 kGy was approximately 40% lower than that of pure silicone rubber), indicating its radiation protection effect. Fluorescence spectra revealed that P_C343 regained strong fluorescence characteristics through radical capture. The fluorescence intensity of SR-P increased with the increasing dose after irradiation, and the aging behavior from 500 Gy to 5 kGy could be sensitively characterized. The experiments demonstrated that the introduction of P_C343 simultaneously achieves dynamic protection against irradiation aging and real-time monitoring in silicone rubber. This strategy provides a novel approach for improving the service reliability of silicone rubber in radiation environments.