Glass construction 50P2O5–30Na2O–10CaO–(10-x)Al2O3–(x)Sm2O3, with x ranging from 0 to 8 mol%, and various Sm2O3 (x) concentrations, were created using the standard melt annealing method. The impact of Sm3+ ions in the produced glass network has been investigated using combined structural and optical properties. We looked at structural and optical factors like density, molar volume, and other optical properties. It was demonstrated that glassy samples are amorphous using X-ray diffraction. Empirical and experimental densities and molar volume were found to be having the same trend with increasing Sm2O3 contents. Fourier transform infrared absorption spectra (FTIR) have been carried out and analyzed using the deconvolution analysis route. Notable changes were observed within the fingerprint region from 450 cm–1 to 1700 cm–1 and prominent peaks were assigned to their respective phosphate vibrational groups. UV–VIS–NIR spectral data were plotted and different optical parameters such as optical energy gap, absorption and extension coefficients were calculated and interpreted in terms of direct and indirect transitions and correlated to their respective structural variations and state of samarium ions.