The emission spectra of Cu and/or Sn doped sodium borate glasses were investigated for controlled glass structure. The results demonstrate that emission of metal ions was enhanced with increasing of B2O3 content. The broad emission band centered at 450 nm and 400 nm reflecting the reduction ability of the borate glass structure is attributed to the low valence state of metal ions Cu+, Sn2+ respectively. The reduction ability of the glass structure was identified by the increasing Sn2+ proportion through XPS measurements. Moreover, the Cu– Sn co-doped sample exhibits remarkably enhanced Cu+ ions emission which reveals the Sn2+ strong reduction effect on the Cu2+ ions. The effect of the structure variation on the mechanism of metal ions luminescence in borate glasses has been discussed.