Surface functionalization of the Ar plasma-pretreated SiLK coating on (100)-oriented silicon wafer (SiLK-Si substrate) via graft modification with viologen (1,1'-substituted-4,4'-bipyridinium salt) was carried out. The method involved a two-step process whereby 4-vinylbenzyl chloride (VBC) was first graft copolymerized, via UV induction, on the Ar plasma-pretreated SiLK-Si substrate surface (the VBC-g-SiLK-Si surface). The benzyl chloride groups of the grafted VBC chains were subsequently coupled with viologen (the viologen-g-SiLK-Si surface). The surface composition and topography of the graft-functionalized SiLK-Si substrates were characterized by X-ray photoelectron spectroscopy and atomic force microscopy, respectively. Pd(II) and Au(III) ions could be adsorbed onto the viologen-g-SiLK-Si surfaces and subsequently reduced to their respective metal atoms under UV irradiation. Electroless deposition of copper could be carried out effectively on the viologen-g-SiLK-Si surfaces with the photoreduced palladium metal. The 180degrees-peel adhesion strength of the electrolessly deposited copper with the viologen-g-SiLK-Si surface reached about 5 N/cm. Thus, not only did the surface grafted viologen molecules provide the chemisorption sites for the photoreduction of the palladium catalyst, they also served as adhesion promoters for the electrolessly deposited copper. (C) 2003 The Electrochemical Society.