Highly active and reusable polymeric catalysts were produced by a self-assembly process of non-cross-linked amphiphilic polymeric ligands with inorganic species. Thus a new insoluble tungsten polymeric catalyst PWAA 1 was prepared from H(3)PW(12)O(40) and poly[(N-isopropylacrylamide)-co-(acrylamide with ammonium salt)], which was suitable for the oxidation of alcohols, amines, and sulfides in aqueous hydrogen peroxide. A new insoluble palladium polymeric catalyst PdAS 2 was produced by self-organization of (NH(4))(2)PdCl(4) and poly[(N-isopropylacrylamide)(10)-co-diphenylphosphinostyrene], which is an excellent recyclable catalyst for the Suzuki-Miyaura reaction in water, water-organic solvents, and organic solvents. It is commercially available from Tokyo Kasei Kogyo (TCI). An improved insoluble palladium polymeric catalyst PdAS-V 3 was assembled from (NH(4))(2)PdCl(4) and poly[(N-isopropylacrylamide)(5)-co-diphenylphosphinostyrene], providing a reusable system for the Mizorogi-Heck reaction. A solid-phase titanium asymmetric polymeric catalyst TiSS 4 was made from Ti (O-i-Pr)(4) and poly(styryl-linked binaphtholate-co-styrene) which promotes an enantioselective carbonyl-ene reaction as a recyclable catalyst.