A method of orienting microphase-separated domains is disclosed, comprising applying a composition comprising an orientation control component, and a block copolymer assembly component comprising a block copolymer having at least two microphase-separated domains in which the orientation control component is substantially immiscible with the block copolymer assembly component upon forming a film; and forming a compositionally vertically segregated film on the surface of the substrate from the composition. The orientation control component and block copolymer segregate during film forming to form the compositionally vertically-segregated film on the surface of a substrate, where the orientation control component is enriched adjacent to the surface of the compositionally segregated film adjacent to the surface of the substrate, and the block copolymer assembly is enriched at an air-surface interface.