In the current work, ytterbium oxide (Yb2O3) powders with the europium (Eu3+) were synthesized by the epoxide-driven sol-gel process. Yb2O3-europium xerogels were synthesized at different molar ratios (0, 2, 5, 8, 10, 20, 30, 40, and 50 mol%) and heat-treated at 1273 K in order to yield a dense crystalline material. The powders were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescent studies were performed to establish the relationship between their structural and luminescent properties. After a 1273 K heat treatment, the resultant powders consisted of spherical particles and presented different phases with well-defined reflections characteristic of a cubic-type crystalline structure, with crystallite sizes ranging from 14 to 30 nm. Finally, according to the luminescence studies, emission bands between 550 and 700 nm, due to the D-5(0) -> F-7(2) transition level of the europium ion, were searched using wavelengths of 612 and 364 nm for excitation and emission, respectively.