B2O3–CaO–Al2O3–ZnO–MoO3 luminescent glasses doped with Dy3+, Sm3+, and Dy3+/Sm3+ were prepared by melt-quenching method. Structure, luminescence properties, energy transfer and thermal stability of the glasses were analysed. As deduced from the increase in density, [BO4] unit proportion and Dy3+ luminescence yellow/blue ratio and the decrease in band gap value, the increase in the doping concentration of Sm2O3 promotes the formation of non-bridging oxygen and enhances the structural asymmetry. Meanwhile, the change in Dy3+ emission intensity and the decrease in fluorescence lifetime indicate the presence of an energy transfer from Dy3+ to Sm3+, and the Inokuti-Hirayama model fit suggests that the energy transfer may occur within the Dy3+-Sm3+ cluster. In addition, the CIE chromaticity coordinates and correlated colour temperature of the Dy3+/Sm3+ co-doped B2O3–CaO–Al2O3–ZnO–MoO3 glass fall within the white light region and have good thermal stability, which is potentially promising for application in W-LED lighting.