Micro/nanolayer coextrusion was used to fabricate polycarbonate (PC)/poly(vinylidene fluoride) (PVDF) layered films with significantly reduced dielectric losses while maintaining high energy density. The high-field polarization hysteresis was characterized for layered films as a function of PVDF layer thickness (6000 to 10 nm) and composition (10 to 70 vol % PVDF), and was found to decrease with decreasing layer thickness and PVDF content. To gain a mechanistic understanding of the layer thickness (or nanoconfinement) effect, wide-angle X-ray diffraction, polarized Fourier transform infrared spectroscopy, and broadband dielectric spectroscopy were employed. The results revealed that charge migration, instead of dipole flipping, was responsible for the hysteresis in multilayered films. The absence of PVDF dipole-flipping was attributed to the nonuniform electric field distribution in the layered structure, where the field in PVDF layers were calculated to be significantly lower than that in PC layers due to large contrast in dielectric constant (similar to 3 for PC versus similar to 12 for PVDF). The charges were likely to be impurity ions in the form of catalyst residue or surfactants from suspension polymerization. The characteristics of the dielectric spectroscopy relaxation indicated that ions mostly existed in the PVDF layers, and PC/PVDF interfaces prevented them from entering adjacent layers. Therefore, as the layer thickness decreases to nanometer scales, the amount of ion movement, dielectric loss, and hysteresis were decreased. This study provides clear evidence of the nanoconfinement effect in multilayered films, which advantageously decreases the hysteresis loss.