In this study, we report layer thickness effect on the electrical insulation property of polysulfone (PSF)/poly(vinylidene fluoride) (PVDF) multilayer films having a fixed composition of PSF/PVDF = 30/70 (vol./vol.). Breakdown strength, dielectric lifetime, and electrical conductivity were studied for 32- and 256-layer films having various total film thicknesses. Among these films, those having thinner PVDF and PSF layers exhibited lower breakdown strength, shorter lifetime, and higher electrical conductivity than those having thicker layers. These experimental results were explained by Maxwell-Wagner-Sillars interfacial polarization due to contrasts in dielectric constant and electronic conductivity for PVDF and PSF, respectively. When both PVDF and PSF layers were thick (ca. > 100-200 nm), more space charges were available in PVDF and no electronic conduction was allowed for PSF. These accumulated interfacial charges could serve as effective traps for injected electrons from metal electrodes under high electric fields. As a result, reduced electrical conductivity and enhanced breakdown strength/dielectric lifetime properties were obtained. When both layers were thin (ca. < 100 nm), fewer space charges were available in PVDF and significant electronic conduction through PSF resulted in low interfacial polarization. Consequently, higher electrical conductivity, lower breakdown strength, and shorter lifetime were observed. These results provide us insights into potential physics to enhance electrical insulation property of polymer films using a multilayered structure having large dielectric constant contrast. (C) 2013 Elsevier Ltd. All rights reserved.