The current study investigates the physical structural and radiation shielding capabilities of a newly developed glass system incorporating silica extracted from rice straw ash (RSA). The purity and chemical composition of the silica are determined using XRF. XRD confirms the amorphous character of the synthesized glass. Moreover, molar volume, optical parameters, and density will be investigated. Gamma (γ)-rays shielding parameters like half-value layer, mass attenuation coefficient, the effective atomic number, and the mean free path are experimentally measured across a broad range of gamma-ray energies (81 keV–1408 keV) emitted from 152Eu, 133Ba, 137Cs, and 60Co radioactive isotopes. The exposure buildup factor will be evaluated with the geometric progression fitting approximation. In addition, Phy-X/PSD software is used to calculate theoretically the former shielding parameters. A good agreement between theoretical and experimental values has been revealed. Finally, a comparison was made to investigate the potential use of our glass to replace the common shielding material like concrete (ordinary and hematite-serpenite), commercial glass (RS 253), and the newly developed Ag2O doped boro-tellurite glass. The newly prepared glass has higher MAC, Zeff values and lowered HVL and MFP values. These properties make our prepared glass system superior in terms of shielding from γ-rays.