Mössbauer spectroscopy analysis and gamma (γ)-ray shielding performance for some iron phosphate glasses with composition 50 %P2O5 + 20 %Na2O + 20 %Fe2O3 + 10 %X, whereX = As2O3, SrO, BaO, CdO, and Sb2O3 w.t.% were investigated. The melt quenching technique was used for glass sample preparation, where the XRD patterns investigated the amorphous nature of the prepared glasses. Moreover, SEM and EDS mapping were used to provide information on the element distribution of the added heavy metals. Mössbauer spectroscopy showed that, most of the iron is present in the glass as Fe3+oxidation state, which is composed of tetrahedral and octahedral coordination states. The remaining iron ions have the form Fe2+ which occupied the tetrahedral coordination state. The γ-ray attenuation parameters like, mass attenuation coefficient (MAC), half value layer (HVL) and the effective atomic number (Zeff) were experimentally measured at different γ-ray energies using 133Ba, 137Cs, and 60Co radioactive sources. Results indicated that the sample containing Sb2O3 is the best-modified glass for gamma radiation protection.