The authors report on the UV‐excited photoluminescence measured in Sb2O3–ZnO–P2O5 glass. Pre‐heat treatment performed before melting effectively prevented the discoloration caused by precipitation of Sb nanoparticles. Although both Sb3+ and Sn2+ belong to the ns2‐type emission center, the Sb3+‐doped 60ZnO–40P2O5 glass showed an emission with a weaker intensity and a broader band than Sn2+‐doped 60ZnO–40P2O5 glass. The emission decay of 1.0SbO3/2–60ZnO–40P2O5 glass was about 2.5 μs, which was shorter than that of 1.0SnO–60ZnO–40P2O5 glass. The obtained results suggest that the emission properties of ns2‐type emission centers depend on several factors, such as element of emission center, chemical composition, and preparation scheme, which are easily and widely tuned in random amorphous materials.