One of the most interesting wide-bandgap semiconductor is 4H-SiC that has an indirect wide-bandgap of 3.3 eV. This material holds great potential to develop power devices that find applications in the field of high-voltage and high-temperature electronics and harsh environments. In this study, we employed complementary noninvasive characterization techniques, including micro-Raman, optical absorption, steady-state, and time-resolved photoluminescence spectroscopy, to investigate the characteristics of a 12 μm thick epitaxial layer of 4H-SiC grown on 4H-SiC. Furthermore, we explored the impact of ionizing radiation on this material, utilizing β-rays and two x-ray sources. The doses are in the range of 1–100 kGy for electrons with energy of 2.5 MeV, 16 kGy for the first x-ray source (an x-ray tube with a W target operating at an anode bias voltage of 28 kV), and 100 kGy for the second x-ray source (an x-ray tube with a W target operating at an anode bias voltage of 100 kV). When exposed to the electron beam, the excitonic band at 3.2 eV exhibits a reduction in its lifetime as the deposited dose increases. In particular, in samples characterized by a greater amount of native defects, both extended and point defects, this effect becomes evident at lower deposited doses. Conversely, in the samples subjected to x-ray irradiation, these effects are not observed. These findings indicate that electron beam irradiation triggers the formation of defects associated with atomic displacement. Ultimately, we have examined the impact of thermal treatments in air, ranging from 100 to 900 °C, to investigate the recovery characteristics of 4H-SiC.