The effect of introducing a multilayer microstructure on the dielectric properties of polymer materials is evaluated in 32- and 256-layer films with alternating polycarbonate (PC) and polyvinylidene-hexafluoropropylene (coPVDF) layers. The permittivity, dielectric loss, dielectric strength, and energy density were measured as a function of the relative PC/coPVDF volume concentrations. The permittivity follows an effective medium model while the dielectric strength was typically higher than that predicted by a volume fraction based weighted average of the components. Energy densities as high as ∼14J∕cm3, about 60% greater than that of the component polymers, are measured for 50% PC/50% coPVDF films.