Eu3+ doped CaWO4 phosphors of different concentrations are prepared by a co-precipitation method. The X-ray diffraction patterns and field emission scanning electron microscopy images are investigated. The excitation spectra, emission spectra and the curves of fluorescence decays of the samples are measured. The Judd-Ofelt (J-O) parameters, quantum efficiencies of the 5D0 level of Eu3+ and color coordinates are calculated. The dependences of relative intensity of charge transfer band, J-O parameter and quantum efficiency on doping concentration are discussed. The photoluminescence properties of Eu3+ doped CaWO4 luminescent material are studied. The results indicate that the 616 nm red emission of Eu3+5D07F2 transition can be effectively excited by 394.5 nm and 465 nm with high excitation efficiency and the concentration quenching is high. So the CaWO4: Eu red phosphor may have a potential application for white light emitting diode.