In this paper, the microwave irradiation process was conducted during the Poly(vinylidene fluoride) (PVDF) nano-composite film fabrication process to analyze how the beta-crystalline is increased. TiO2 was added as a nanoparticle reinforcement to further improve the beta-crystalline conformation of the PVDF films by van der Waals force due to the difference of electronegativity between PVDF and the metal oxide nanoparticle. The crystalline conformation of the fabricated films was analyzed by X-ray diffraction and Fourier transform infrared spectroscopy. According to these analysis results, it was confirmed that the microwave irradiation process during the solvent evaporation process increases the crystallinity of the PVDF films, and more beta-crystalline can be obtained after additional film stretching process. It was also found that the PVDF nano-composite films with the metal oxide have relatively higher beta-crystalline conformation rather than the neat PVDF films.