Bismuth-oxyfluoride glasses with the chemical composition of P2O5+NaF+SiO2+Bi2O3 (PNSiBi) have been prepared by melt-quenching method and studied their structural and thermal properties through Raman, Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) and differential thermal analysis. Moreover, elemental analysis of these glasses has been performed with energy-dispersive X-ray (EDX) spectroscopy. The glass transition and crystalline temperatures of the glasses have been estimated using differential thermal analysis (DTA). The vibrational modes of these glasses have been studied through Fourier transform infrared (FTIR) and micro-Raman analysis. Elemental compositions and binding energies of the PNSiBi glasses have been explored from XPS analysis. Binding energies of PNSiBi glasses have been obtained as 100 eV for Silicon (Si2p), 132 eV for Phosphorous (P2p), 157 and 163 eV for Bismuth (Bi 4 f) and 1069.7 eV for Sodium (Na1s). The valance states and binding energies of these elements unveiled orthophosphate (PO4)2− type structure, which forms trisodium phosphate [Na3(PO4)] with sodium and fluorides of BiF3, and (PF6)−. A 1 mol% Sm2O3 doped PNSiBi05Sm01 glass unveiled robust emission among other concentrations of Bi ions proposed that PNSiBi05 glass could be an effectual host for laser and other active photonic applications.