We investigate the enhanced alignment of lamellar microdomains under an electric field by addition of lithium chloride (LiCl) into polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) copolymers. A significant increase of dielectric contrast resulting from the formation of lithium-PMMA complexes markedly reduces the critical electric field strength required to overcome the preferential interactions of one block with the substrate, providing a route to achieve the complete alignment of microdomains in block copolymer thin films.