Two different morphologies of ZnO (lotus-shaped, rod-shaped) and ZnO/PVDF composite materials were prepared. The morphologies of ZnO and composite materials were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Fourier transform infrared spectroscopy (FT-IR), thermal gravimetry (TG), and X-ray diffraction (XRD) were also used to characterize the chemical structures and phase composites of ZnO and ZnO/PVDF composite materials. Breakdown voltage, dielectric constant and dielectric loss of ZnO/PVDF composite materials were also tested. Microstructure analysis showed that ZnO nanoparticles dispersed uniformly in the matrix. And the dielectric constant expresses a significantly improvement while the dielectric loss and breakdown voltage expresses no significant change. Moreover, dielectric constant keeps an improvement tendency with increasing content of ZnO.