The Er3+ doped lead–bismuth–gallium oxide glasses were prepared by melt quenching technique. The spectral and luminescent properties were analyzed based on experimental and theoretical calculations. Analysis of Er3+ concentration dependences of density and electronic optical polarizability was carried out. The radiative lifetime values for 4S3/2 and 4F9/2 energy states were calculated using Judd-Ofelt theory. In the glassy system under study, the concentration quenching of state 4S3/2 was discovered at content of erbium ions above 0.869 × 1020 cm−3. It was also shown that 4F9/2 energy state was isolated from concentration effects and showed an increase in luminescence intensity with increasing concentration of activator ions. The luminescence quantum efficiency for transition 4S3/2 → 4I15/2 was about 40%, which allows us to consider this system as a glassy matrix effective for activation by rare-earth ions.