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A series of degradable block copolymers, polystyrene-b-poly(l-lactide) (PS–PLLA), with PLLA hexagonal cylinder (HC) morphology has been synthesized in this study. Well-oriented, perpendicular PLLA cylinders of PS–PLLA thin films were efficiently achieved by spin coating using appropriate solvents regardless of the use of substrates. After hydrolysis of PLLA, well-oriented HC nanochannel arrays over large area in addition to uniform surface with controlled thickness and domain size were obtained; providing a simple and efficient path to prepare nanopatterned templates for applications. The induced orientation of PS–PLLA microdomains was strongly dependent upon the evaporation rate of solvent and its solubility between constituted blocks. The origins for the formed perpendicular HC morphology were systematically studied. The primary concern of controlled morphology for nanopatterning is to develop …