Plasma graft polymerization of 4-vinylpyridine (4VP) on Ar plasma-pretreated Si(100) surfaces was carried out. The plasma graft-polymerized 4VP films (pp-4VP films) were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, and atomic force microscopy (AFM). XPS and FTIR results revealed that the pyridine functional groups of the grafted pp-4VP films could be retained, to a certain extent, under proper glow discharge conditions, such as a low input radio frequency power. AFM images revealed that the pp-4VP-grafted Si(100) (pp-4VP-Si) surfaces remained relatively smooth. The grafted pp-4VP film on the Si(100) surface was used not only as the chemisorption sites for the palladium complexes (without the need for prior sensitization by SnCl2) during the electroless plating of copper, but also as an adhesion promotion layer for the electrolessly deposited copper. The electrolessly deposited copper on the pp-4VP- Si surface exhibited a 180degrees-peel adhesion strength above 5 N/cm. The adhesion strength was attributed to the strong interaction of the pyridine functional groups of the pp-4VP layer with palladium and copper, the spatial distribution of the pp-4VP chains on the Si(100) surface and into the metal matrix, and the fact that the pp-4VP chains were covalently tethered on the Si(100) surface.