The present work studies the influence of cobalt chloride (CoCl2) and γ-irradiation dose on the optical, thermal properties, and dynamic mechanical analysis (DMA) of different blends of (PVA/PEG /PVP). Different optical parameters were deduced before and after γ-irradiation with different doses (5, 10, and 15 kGy). The optical conductivity (σoptical) values for the prepared blends and composites indicate their importance for optical energy applications, especially after γ-irradiation. Modifying and enhancing the refractive index of γ-irradiated samples enables their use in various optical devices. Linear optical susceptibility (χ(1)) and the third nonlinear susceptibility (χ(3)) increased by decreasing the PVA amount in the blend and composites. Thermogravimetric analysis TGA confirmed that by adding CoCl2 to the hosting blends, the thermal oxidative degradation energy Ea became much higher than unirradiated samples. The DMA results show that the storage modulus was significantly improved after adding CoCl2 and after irradiating the samples by 5 and 10 kGy. Also, all the samples exhibited two relaxation temperatures and were greatly affected by adding the filler.