<p>Alkali-modified oxyfluoride boro-phosphate glasses with the novel chemical composition 30B₂O₃+24P₂O₅+15ZnF₂+15SrF₂+15MO+1Sm₂O₃, (where MO = Na₂O, NaF, Li₂O, LiF, K₂O, KF) were synthesized using the melt-quenching technique to investigate the influence of oxide and fluoride modifiers on the glass network. The novelty of the present study lies on the effect of alkali oxide and fluoride modifiers in the boro-phosphate glass system to tune optical bandgap, elastic rigidity and gamma ray attenuation behavior. The FTIR and EDX studies confirm the presence of borate and phosphate structural units and reveal the role of modifiers in the glass network. Density, molar volume and refractive index demonstrate that oxide modifiers enhance the structural compactness. Elastic studies reveal improved rigidity in oxide modifier incorporated glasses. TGA studies reveal that the prepared glasses possess good thermal stability and at higher temperatures degradation depends on the nature of alkali modifier. UV-Vis-NIR spectrum displays the characteristic 4f−4f transitions of Sm³⁺ ions, while optical bandgap and Urbach energy analyses provide insight into the electronic structure and degree of disorderliness respectively. Gamma ray attenuation parameters were also evaluated employing the MCNP simulation over the energy range of 0.0332–1.408&#xa0;MeV, demonstrating the fact that the type of modifier play a critical role in governing the photon interaction behavior. The result ascertains a clear structure-property relationship and highlights the effectiveness of controlled oxide/fluoride substitution in designing the multifunctional glass materials for radiation shielding applications.</p>