Red emitting phosphor Ca-3(VO4)(2):Eu3+ was prepared by citric acid-assisted solution combustion method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and fluorescence spectrophotometer. The influences of Ca to V molar ratio and synthesis temperature on phase composition, morphology, grain size, photofluorescence properties, and ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS) of as-synthesized samples were investigated. The results indicate that Ca to V molar ratio play a key role for the changing of phase composition, excitation spectrum, and luminescence intensity. The sample prepared at 900 A degrees C, keeping Ca/V = 3:2.2, has the highest photoluminescence intensity. The possible causes of the effects on photoluminescence mechanism were also discussed in this work.