Luminescent polycrystalline films of CaWO4 and CaWO4:Pb2+ have been prepared on tungsten substrates by applying low anodic potential pulses at tungsten electrodes in alkaline solutions containing calcium ion or calcium and lead ions. Anodically grown CaWO4 films show weak luminescence and broad X-ray diffraction peaks. The luminescence band of the film is shifted toward a longer wavelength (red shift) compared with that of the CaWO4 powder prepared by a conventional solid-state method. By postannealing the anodically gown CaWO4 film at high temperatures, luminescence intensities are enhanced, and the luminescence band maximum has been blue shifted to 420 nm. CaWO4 films doped with a trace amount of Pb2+ ion, electrochemically prepared in alkaline solutions containing calcium and lead ions, show a decrease in the intensity of luminescence maybe because of hydroxides or of hydrated water. By postannealing, the intensity of luminescence is enhanced dramatically, and the luminescence band maximum is red shifted to 444 nm in comparison to that of undoped CaWO4 films.