Sandwich-structured BaTiO3/poly(vinylidene fluoride) (PVDF) nanocomposites are successfully prepared by the solution-casting method layer by layer. They possess both high breakdown strength and large dielectric polarization simultaneously. An ultra-high energy-storage density of 18.8 J cm(-3) can be achieved by adjusting the volume fraction of ceramic fillers: this is almost three times larger than that of pure PVDF.