The reaction of reactive alkali metal organometallic derivatives of divinylbenzene-cross-linked polystyrene with solutions of dichloro(l,5-cyclooctadiene)palladium(II) to form palladium/polystyrene catalysts is described. Organometallic polymers used in these reactions include polystyryllithium, polystyrylbenzyllithium, poly-styrylphenyl(trimethylsilyl)methyllithium and polystyrene-bound sodium anthracene. The palladium/polystyrene catalysts formed in these reactions were characterized by ESCA and electron microscopy, and their activity as hydrogenation catalysts was examined in various solvents and under various conditions of catalyst pretreatment. Comparisons of the catalytic activity of these catalysts to commercial Pd/C in the hydrogenation of various substrates are also made. Novel catalytic activity observed for these palladium/polystyrene catalysts includes some activity as decarbonylation catalysts in reactions with simple alkyl and aryl aldehydes and their use in place of tetrakis(triphenylphosphine)palladium(0) as a catalyst for the formation of tertiary allylamines from allyl esters and secondary amines. The interaction of functional groups such as organolithium and carboxylic acid groups attached to the polystyrene support with the active centers of the hydrogenation catalysts was also demonstrated by their effect on the activity of these hydrogenation catalysts. 1983, American Chemical Society. All rights reserved.