It is hardly possible to obtain rare earth doped CaWO4 thin films directly through electrochemical techniques. A novel post processing has been proposed to synthesize CaWO4:Eu3+ thin films at room temperature. X-ray diffraction, X-ray photoelectron spectrometry, spectrophotometer were used to characterize their phase, composition and luminescent properties. Results reveal that Eu3+-doped CaWO4 films have a tetragonal phase; the content of Eu in the near surface region is much higher than that of the bulk; under the excitation of 310 nm, a sharp emission peak at 616 nm has been observed for Ca0.9WO4:Eu0.13+ thin films.