The effect of Bi2O3 and PbO on the physical and luminescence properties of Eu3+:PbO–Bi2O3–WO3–B2O3 glasses is presented. The increase in the concentration of Bi2O3 causes UV shift in the optical absorption spectra and increase in the intensities in the photoluminescence spectra (excitation and emission) of these glasses. The spectroscopic ratio factors of the integrated luminescence intensities 5 D 0 → 7 F J / 5 D 0 → 7 F 1 (j = 0, 1, 2, 3) are reported. The experimental branching ratios of the 5 D 0 → 7 F J (j = 0, 1, 2, 3) are presented. The 5 D 0 → 7 F 2 exhibits high β R (>60 %) values for all glasses reflecting their potential lasing application in the development of red laser and optical devices. The σ e for 5 D 0 → 7 F 2 and 5 D 0 → 7 F 4 transitions are reported. The observed 5 D 0 → 7 F 0 in the emission spectra confirms low symmetry around Eu3+ ion for all glass compositions.