This article describes a strategy to fabricate a conducting polymer and complementary gold microstructures through selective electrodeposition and wet chemical etching on a chemically tethered polymer brush template that is prepared by surface-initiated atomic transfer radical polymerization (ATRP) and subsequent photopatterning. The polymer brush acts as a sufficient insulating barrier and thus the polypyrrole (PPy) can be grown from the exposed area of the polymer brush template. Different polymer brushes provide different protection actions in selective etching, which is utilized to generate complementary (negative or positive) gold pattern on a single template in different manners.