This article reports the preparation and derivation of chemically tethered polyhydroxyethylmethacrylate (PHEMA) brush and its application in microfabrication. PHEMA brush was prepared by the surface-initiated atomic transfer radical polymerization and derived by either organic reaction or sequence polymerization. The differential etching process was studied by atomic force microscope (AFM) and optical micrograph. PHEMA brush cannot prevent the underlying gold from dissolving in aqueous etchant KI/I-2 solution. Differential etching of UV-patterned PHEMA template resulted in metal (gold) rings. (c) 2007 Wiley Periodicals, Inc.