In this work, the role of europium doping of glasses formulated in the ternary system ZnO–CdO–TeO2 is described. The Eu-doped oxide glasses were prepared by the conventional melt-quenching method and by using three different compositions. Structural studies reveal that there exists a good affinity between Cd and some rare earth (RE) ions to form the crystalline phase. The X-ray diffraction (XRD) diagrams display that the structure of these glasses is amorphous and with the increase in CdO content and the compatibility of Eu3+, there is a tendency to form nanocrystals of CdTe2O5. The scanning electron microscopic (SEM) observation of their microstructure confirms the presence of phase separation. Differential thermal analysis (DTA) of these glasses showed small exothermic peaks noted around 450°C for the V2 glass and 480°C for V1 and V3 glasses, which could be attributed to the formation of these crystals. The infrared spectra showed a main absorption band around 800–600 cm−1 corresponding to the Te–O stretching mode in TeO4 and TeO3 groups. By optical absorption (OA), the band gap (Eg) for each glass was determined; these values were 3.27, 3.14, and 3.3 eV for the V1–V3 glasses, respectively. Furthermore, the presence of Eu3+ was detected in the 370–470 nm short-range wavelengths. The photoluminescence (PL) experiments of the glasses showed light emission due to the following transitions: 5D0 → 7F1, 5D0 → 7F2, 5D0 → 7F3, and 5D0 → 7F4.