Europium- and copper-doped calcium vanadates with the general formula Ca3-1.5x-yEuxCuy(VO4)2 (x = 0, 0.075; y = 0, 0.06 and 0.18) were synthesized by the solid state reaction. Synthesized materials were analyzed by the powder X-ray diffraction (PXRD), UV–Vis, Raman, luminescence spectroscopy, and colorimetry. Unit cell dimensions of the obtained samples were analyzed by the Rietveld refinement of the PXRD data. The crystal symmetry corresponds to the R3c group. Europium-doped samples exhibited luminescent properties, typical for the majority of europium-containing inorganic compounds. Additional copper-doping partially suppressed the europium luminescence. The europium-and-copper-doped samples possess bright yellow colors. Thus, obtained materials are perspective for the application as inorganic yellow pigments.