Hexagonally arranged PEO cylinders in the PEOm-b-PMA(Az)(n) thin film were perpendicularly oriented on Si wafer substrates with a wide range of water contact angle (<5 degrees to 85 degrees) by controlled modification with octadecyltrichlorosilane (OTS). Additionally, the film was stiffly adhered on the modified substrate due to an anchoring effect of partly covered monolayer of OTS.