There is a need in electronic systems and pulsed power applications for capacitors with high energy density. From a material standpoint, capacitive energy density improves with increasing dielectric constant and/or breakdown strength. Current state-of-the-art polymeric capacitors are, however, limited in that their dielectric constant is low (2–4). Our approach to improve polymer film capacitors is to combine, through microlayer coextrusion, two polymers with complementary properties: one with a high breakdown strength (polycarbonate) and one with a high dielectric constant (polyvinylidene fluoride-hexafluoropropylene). As opposed to the monolith controls, multilayered films with various numbers of layers and compositions subjected to a pulsed voltage exhibit treeing patterns that hinder the breakdown process. Consequently, substantially enhanced breakdown strengths are measured in the mutilayered films. It is further shown, by varying the overall film thickness, that the charge at the tip of the needle electrode is a key parameter that controls treeing. Based on the acquired data, a breakdown mechanism is formulated to explain the increased dielectric strengths. Using the understanding gained from these systems, selection and optimization of future layered structures can be carried out to obtain additional property enhancements.