In the present investigation, conventional melting techniques were employed to fabricate the fluorophosphate glass composites with a composition of 20NaF–60P2O5–20Na2O–3Fe2O3 (mol.%). An investigation was conducted to analyze the impact of various doses of gamma-ray irradiation on certain optical properties. The alteration in the localized defects caused by gamma irradiation can explain the reduction in the refractive index (n) as the doses of gamma-ray irradiation increase, up to 10 kGy. The results of the solar skin protection factor (SSPF) and solar material protection factor (SMPF) tests demonstrate that the un-irradiated composite offers the highest level of protection against the harmful effects of solar energy on both human skin and materials. Some optical parameters, such as the concentrations of the charge carrier (Nopt), the relaxation time (τ), the optical electronegativity (ηopt), and the optical mobility (μopt) showed gamma dose-dependent. The effects of gamma-ray irradiation on the composites were analyzed using Electron Spin Resonance (ESR) and Fourier Transform Infrared (FTIR) spectroscopic studies, both before and after exposure to 10 and 20 kGy.