In this study, the structural, thermal, photoluminescence, and optical properties of PVA/Gd₂O₃ nanocomposite film with different doses of gamma irradiation (0, 15, 30, 45, and 100 kGy) were studied. The Gd₂O₃ nanoparticles (NPs) were prepared via the co-precipitation technique, and PVA/Gd₂O₃ nanocomposite film was obtained via the solution casting method. The XRD data demonstrated the successful fabrication of Gd₂O₃ NPs and PVA/Gd₂O₃ nanocomposite film. Also, EDX spectra verified the elemental composition of PVA/Gd₂O₃ nanocomposite film. SEM images illustrated the surface morphology of the studied films. Additionally, a remarkable influence of gamma irradiation on thermal stability has been detected. Four prominent photoluminescence peaks were observed for the PVA/Gd₂O₃ nanocomposite films. Also, the energy gap decreases as the dose of gamma rays increases from 15 to 45 kGy and suddenly increases in the case of 100 kGy. Also, the Urbach’s energy increases from 3.65 eV for un-irradiated PVA/Gd₂O₃ nanocomposite film to 6.9 eV at a dose of 45 kGy. Overall, the thermal stability, optical, and photoluminescence properties of irradiated PVA/Gd₂O₃ nanocomposite films make of them suitable materials for flexible optoelectronic devices.