Linear polymer brush structures of poly(methacrylic acid) chains, exhibiting a width from several hundred to 20–30 nm and a controllable height (nano-“hedge”), were grafted from designer substrates by photopolymerization using thiol-based iniferters assembled on Au nano-lines. The Au nano-lines were obtained using H-terminated silicon substrates by AFM tip assisted (“dip-pen”) nanolithography of HAuCl4 which yielded Au nano-wires upon reduction in contact with the substrate. The polymeric nano-“hedge” structures were characterized by AFM.