Hexagonally arranged nanocylindrical arrays of polymercomplexed multivalent metallic ions were fabricated by performing template process with amphiphilic diblock copolymer consisting of poly(ethylene oxide) and liquid crystalline poly(methacrylate) with azobenzene mesogen (PEO-b-PMA(Az)). The block copolymer exhibits PEO hexagonal cylindrical microdomains perpendicular to the substrate. Lead ions were selectively diffused into the PEO microdomains to generate the lead-doped nanocylinder array, of which size, shape, and alignment can be controlled by the block copolymer thin film as a template.