In this study, we investigate the effect of added interfaces on the dielectric and breakdown response of polyvinylidene fluoride polymer (PVDF). Multilayer laminates (1 through 4 layers) of PVDF are fabricated using hot pressing. A series of electrical characterization techniques including high voltage breakdown, dielectric spectroscopy and impedance spectroscopy, show the effect of interfacial elements on dielectric breakdown strength (displaying an 18% increase from a 1-layer to 3-layer structure) and dielectric permittivity (increasing 10% from 1- to 4-layers). Equivalent circuit modeling of impedance data is used to characterize the effect of laminated interfaces at low frequencies (10 mHz) and elevated temperatures (70 °C). Results suggest capacitive circuit elements in addition to a Debye like bulk model are necessary to describe space charge polarizations observed in multilayered structures. Better understanding the effect of added interfaces on charge transport in all organic laminates will provide insight into conduction through organic dielectric media, and offer insight into improving energy density and mitigating loss in high energy storage applications.