The ion Er 3+ was introduced into a new kind of glassy matrices prepared from a mixture of CdO–ZnO–V 2O 5 and Er(NO 3) 3·5H 2O as source of Er 3+ ions. The obtained glasses were characterized by infrared spectroscopy and micro photoluminescence and micro Raman spectroscopies. The glass formation process produced Al diffusion from the crucible to the oxides mixture yielding crystalline micro aggregates. The room temperature photoluminescence spectra showed transitions from different Er 3+ levels in the 450–900 nm range. In particular, the 4F 9/2 → 4I 15/2 transitions were strongly affected by local electric fields since these transitions presented Stark effect splittings whose intensity was dependent on the atomic order surrounding the Er 3+ ions. It was found that a highly reproducible multiplet emission was particularly strong in crystalline micro-regions of Zn x Al 2− x O 3 immersed in the vitreous matrix.