Abstract: Cross-linking polymerization of a trifunctional methacrylate monomer, trimethylolpropane trimethacrylate (TRIM), under controlled conditions yields macroporous polymers bearing surface-accessible unpolymerized methacrylate residues. These residues have been utilized for copolymerization with different functional monomers to obtain composite polymer matrices with surface coatings of functional polymer chains. Poly(TRIM) modified with methacrylamide, N'N-dimethylacrylamide, vinylazlactone, and copper(II) dimethacrylate exhibit useful functional properties that depend on the type of functional monomer used yet retain the desirable physical properties of the original poly(TRIM) matrix. The metal-complexing polymer made by grafting copper(II) dimethacrylate to poly(TRIM) exhibits better accessibility of the metal-coordinating sites compared to its bulk-polymerized counterpart. Similarly, the surface-hydrophilized matrices made by grafting methacrylamide and N'N-dimethylacrylamide show good water absorbency yet exhibit better matrix stability to environmental change compared to corresponding bulk-copolymerized materials. The physicochemical characteristics of these functional polymer matrices were evaluated by C-13 NMR, X-ray photoelectron spectroscopy, IR spectroscopy, and scanning electron microscopy. Poly(TRIM) particles surface-modified by template polymerization of a copper(II)-[N-(4-vinylbenzyl)imino]diacetic acid (6):template complex and ethylene glycol dimethacrylate exhibit selectivity similar to bulk-polymerized templated polymers in rebinding the bisimidazole template