The present invention is directed to photovoltaic devices and methods of generating electrical energy and power therefrom, based on a novel nano-enhanced bulk photovoltaic effect using non-centrosymmetric crystals, including ferroelectric and piezoelectric materials. In certain embodiments, the device comprises a layer of non-centrosymmetric crystalline materials, and a plurality of electrodes disposed in an array upon or penetrating into at least one surface of the crystalline material, the electrodes being optimally spaced to capture the ballistic carriers generated upon irradiation of the crystalline material.