The poly (vinylidene difluoride) (PVDF) has been of great interest for energy conversion of microelectromechanical system devices. A semicrystalline polymer, the PVDF has five crystallographic forms, α, β, γ, δ, and ε. The latter four structures exhibit a permanent dipole moment. In this research, we investigated effects of microstructures of the PVDF on its piezoelectricity for energy harvesting. Using various experimental techniques, we observed the power density generated by a mechanical force that was correlated with the phase transformation between amorphous, α, β, and γ phases. The transformation was time-dependent in a nonlinear manner. Such transformation influences the energy transition and storage of small devices.