A nanoporous polyvinylidene Fluoride (PVDF) thin film was developed for applications in energy harvesting, medical surgeries, and industrial robotics. This sponge-like nanoporous PVDF structure dramatically enhanced the piezoelectric effect because it yielded considerably large deformation under a small force. A casting-etching method was adopted to make films, which is effective to control the porosity, flexibility, and thickness of the film. The films with various Zinc Oxide (ZnO) mass fractions ranging from 10 to 50% were fabricated to investigate the porosity effect. The piezoelectric coefficient d33 as well as dielectric constant and loss of the films were characterized. The results were analyzed and the optimal design of the film with the right amount of ZnO nanoparticles was determined.