Chemical epitaxy with a density multiplication process was applied to the perpendicularly oriented hexagonal cylinder nanostructure of liquid crystalline block copolymer (PEO-b-PMA(Az)) thin film through thermally induced microphase separation by using a newly designed PMA(Az)(24) brush. The hexagonal lattice orientation with 1.9 tera-cylinders per inch(2) was laterally controlled for long-range-ordered direct self-assembly. Furthermore, the direct pattern-transfer of the assembled structure to an Au nanodot array was demonstrated by doping of HAuCl4 selectively into the PEO cylindrical microdomains and then vacuum ultraviolet light irradiation to cause polymer etching and reduction of the Au ions.