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The possibility of using self-assembled films of block polymers as templates to fabricate nanoscale structures for devices has attracted great attention towards this class of material. Self-assembly of a block copolymer can be directed by using an electric field to orient features (i.e., ~10-nm-diam cylinders) parallel to the electric field, making the material more attractive as a nanoscale lithography mask. In this letter we describe an approach to influence the electric field orientation phenomena by interfacial effects. As a result, the 15-nm-diam polystyrene cylinders of the polystyrene–polyisoprene–polystyrene triblock copolymer orient perpendicular to the electric field. The described approach along with the previous method can produce a directed self-assembly to fabricate complex nanoscale structures with orthogonally oriented nanoscale width lines.