Thin films of CaWO4 were synthesized by pulsed laser deposition (PLD) using targets composed of CaO and WO3 oxide mixtures. The crystallinity of CaWO4 thin films strongly depended on PLD conditions, that is, substrate temperature, ambient oxygen pressure, and laser fluence. Congruent thin films with stoichiometry were obtained at 873 K. They showed photoluminescence (PL) at room temperature. PL spectra were characteristic with excitation wavelength, peaked at 440 and 520 nm, which were excited with 340-360 and 300-330 nin, respectively. Cathodeluminescence (CL) spectra could be recorded at room temperature on the PLD thin films and were composed of the same species as observed in PL spectra. Intensity of CL spectra increased drastically after postannealing the PLD thin films at 873 K. PLD experiments were also carried out using CaWO4 targets at the same conditions. Crystalline CaWO4 thin films were obtained much easier than PLD using targets composed of CaO and WO3 oxide mixtures.