Stoichiometric CaMoO4 thin film was successfully fabricated based on chemical solution processing. The thin films were deposited on Si(100) substrates by means of the spin-coating technique. X-ray diffraction reveals that the CaMoO4 thin film prepared are pure and well crystalline thin films. Atom Force Microscope photographs indicate that the film prepared possesses a homogeneous and dense surface morphology. The average grain size of the films was 40-50 nm, and the root-mean-square (RMS) of the surface roughness and the average surface roughness of the film measured were 2.161 nm and 1.726 nm respectively. The photoluminescent properties of calcium molybdate thin film under ultraviolet light excitation were systematically measured from 12 K to room temperature and a green emission band of the films were observed. The results of present work confirm that the chemical solution processing is a promising technology on the fabrication of CaMoO4 thin film.