A layered structure comprising a self-assembled material is formed by a method that includes forming a photochemically, thermally and/or chemically treated patterned photoresist layer disposed on a first surface of a substrate. The treated patterned photoresist layer comprises a non-crosslinked treated photoresist. An orientation control material is cast on the treated patterned photoresist layer, forming a layer containing orientation control material bound to a second surface of the substrate. The treated photoresist and, optionally, any non-bound orientation control material are removed by a development process, resulting in a pre-pattern for self-assembly. A material capable of self-assembly is cast on the pre-pattern. The casted material is allowed to self-assemble with optional heating and/or annealing to produce the layered structure.