The effect of glass powder on the UV-Vis spectroscopy of polyvinyl alcohol (PVA) has been studied. The glass powder was obtained from fluorescent tubes waste. The solution casting method was utilized to prepare PVA- glass composite films by adding glass powder with 10, 20, 30, and 40 wt. %. UV-Vis absorption spectra of PVA- glass samples were listed in the range 200–1100 nm at room temperature. The optical parameters were calculated as follow: transmittance, absorption coefficient, extinction coefficient, refractive index, dielectric constant, and dielectric loss. The results of XRD showed that the amorphous nature was observed to increase with increase in the concentration of the added glass powder. The transmittance increased with the wavelength and the large increase in the weight percentage of glass powder made the transmittance constant for a certain range of wavelengths. While the absorption coefficient generally decreased with increasing wavelength. Also it was observed that at wavelengths greater than 600 nm, the absorption coefficient increased with the increase in the weight ratio of glass powder (except 20 wt. %). Furthermore, the highest values of the absorption coefficient were observed for the sample containing 20 wt. % of glass powder. It was also found that the change in the refractive index and dielectric constant with the wavelength were accompanied by the presence of peaks in the case of the pure sample and the other containing 10 wt% glass powder, while the peaks disappeared when the percentage of glass powder increased. On the other hand, it was noticed that the pure sample has the values of the imaginary dielectric constant and extinction coefficient that change very slightly with the wavelength and had the lowest values, while it increased with wavelength in other samples. Finally it was found that the energy gap did not change by adding glass powder except for the addition of 30% and 40 wt. %. Through this study, it was possible to change the optical properties of the polymer by adding glass powder, which allows the possibility of benefiting from the new formed composites for use in different applications and according to their response to wavelengths.