A novel and cost-effective electrostatic spray-assisted vapour deposition-based method for polymer films with specific surface structure has been developed. Oriented polyvinylidene fluoride (PVDF) thin films were successfully prepared by this novel method. The novel method involves corona spraying of PVDF solution onto a hot substrate. The vaporization of the solvent in the vicinity or on the substrate occurs in the presence of the corona field during the deposition. Cooling down under the corona field after deposition results in a high beta crystallite content of the films. The crystallite films were characterized using a combination of infrared spectroscopy and X-ray diffraction.