Currently, wearable electronics are increasingly widely used, leading to an increasing need of portable power supply. As a clean and renewable power source, piezoelectric energy harvester can transfer mechanical energy into electric energy directly, and the energy harvester based on polyvinylidene difluoride (PVDF) operating in 31-mode is appropriate to harvest energy from human motion. This paper established a series of theoretical models to predict the performance of 31-mode PVDF energy harvester. Among them, the energy storage one can predict the collected energy accurately during the operation of the harvester. Based on theoretical study and experiments investigation, two approaches to improve the energy harvesting performance have been found. Furthermore, experiment results demonstrate the high accuracies of the models, which are better than 95%.