For many applications, the surfaces of the polymeric microstructures must be inert or metallic or chemically tailored. The present work is concerned with the metallization of silicone-rich UV cured polyester. Surface modification of the silicone-rich polyester via argon plasma pretreatment and subsequent UV-induced graft copolymerization with 1-vinylimidazole was carried out to improve the adhesion of electrolessly deposited nickel. The optimum process conditions for argon plasma and UV grafting on the silicone-rich polyester surface were determined. The surface chemistry, energetics, and mechanical roughness of silicone-rich polyester after each step were studied using X-ray photoelectron spectroscopy, contact angle measurements, and atomic force microscopy. The surface-modified silicone-rich polyester was metallized by electroless nickel plating. Scanning electron microscopy results show good Ni/silicone-rich polyester adhesion has been achieved. Based on the conditions optimized in this work, metallized 3D microstructures can be developed. A model study using pure poly (dimethylsiloxane) shows not only the feasibility of electroless nickel plating on pure silicone (and hence the silicone-rich UV curable polyester surface of interest) but also indicates the formation of peroxide or hydroxyl peroxide attached to silicon after argon plasma treatment and aging. (C) 2004 The Electrochemical Society.