Structural and spectroscopic behavior of TeO2-PbO-Eu2O3 glass ceramics containing small amounts of Ag2O (0.5 mol%) or metallic Ag nanoparticles (AgNPs) (0.33 mol%) have been studied by varying their Eu2O3 content (0-10 mol%). The structural behavior of these samples was investigated by means of X-ray diffraction (XRD), SEM microscopy, and Fourier transform infrared (FTIR) spectroscopy. The average unit-cell parameters, crystallites size, and the quantitative ratio of the crystallographic phases in the samples were evaluated based on XRD data. FTIR spectroscopy data revealed that the TeO3 and TeO4 are the main structural units of these glass ceramics and their ratio, TeO3/TeO4, changes as function of the europium oxide content and the codoping of the samples. Luminescence spectroscopy measurements evidenced the important peaks located at 438, 550, and 722 nm due to the Pb2+ ions and at 589 and 611 nm due to the Eu3+ ions present in the studied samples. The presence of AgNPs in the studied glass ceramics determines a considerable enhancement of the luminescence bands of Eu3+ ions from 589 and 611 nm.