A variety of polymer-supported transition metal catalysts that effect unique transformations of various organic substrates has been developed. Platinum asymmetric hydroformylation catalysts supported on polystyrene containing an incorporated asymmetric chelating phosphine ligand yield branched aldehydes from olefins in 98 % enantiomeric excess. Ruthenium catalysts supported on a polyquinoline designed to chelate ruthenium can be utilized catalytically for the selective oxidation of alcohols to aldehydes, and the reaction can be driven electrochemically by coating the polymer containing the catalyst on an anode. Silica polymers, some of which can be prepared by sol-gel processes and containing a chelating phosphine, have been utilized in a number of catalytic reactions. Because silica is a thermally and chemically stable support, it is especially useful for catalytic reactions that must be carried out under severe reaction conditions. Carbon monoxide reduction/ homologation and olefin hydroformylation reactions have been carried out utilizing ruthenium, rhodium and cobalt catalysts on these silica supports.