In this work, the luminescent properties of Sb3+/Mn2+ codoped 60P2O5–40MgO glass are presented. White light photoluminescence combining blue and orange-red light was observed under ultraviolet light excitation. The emission spectra showed that the blue emission intensity of Sb3+ decreased significantly whereas the red emission intensity of Mn2+ increased with the increasing concentration of Mn2+ ions. Meanwhile, by maintaining the concentration of MnO (2.0 mol%) and increasing concentration of Sb2O3, both the blue emission and red emission were enhanced remarkably. The energy transfer from Sb3+ to Mn2+ ions via the dipole–quadrupole interaction was confirmed.