In this paper, an investigation of a vinylidene fluoride-trifluoroethylene (VDF/TrFE) copolymer film for use in a nonpolarized energy harvester is presented. The Fourier transform infrared spectroscopy and X-ray diffraction analysis of a nonpolarized VDF/TrFE copolymer film indicate that polymer crystallinity depends on film thickness. Furthermore, the growth of the polar structure (β phase) is observed upon the reduction in the thickness. However, power generation does not exhibit a linear behavior because the generation capacity increases with the thickness. These results indicate that the film thickness for a nonpolarized harvester must be optimized to obtain the maximum output.