Copolymer products were prepared by radiation grafting of 4-vinylpyridine onto films of low-density poly(ethylene) and poly(tetrafluoroethylene) (PE-graft-P4VP and PTFE-graft-P4VP, respectively). The corresponding metal complexes were in turn obtained by interaction of the radiation-grafted copolymers with aqueous solutions of various salts such as FeCl3 center dot 6H(2)O, COCl2 center dot 6H(2)O, VOSO4 center dot 5H(2)O, Na2MoO4 center dot 2H(2)O and Na2WO4 center dot 2H(2)O at room temperature. The content of metal ions was found to be within 0.53-10.93 mg metal/g polymer carrier. The polymer-supported metal complexes were identified by infrared spectroscopy and electron paramagnetic resonance analyses. The structure of the iron-containing polymeric materials was evaluated by Mossbauer spectroscopy. Some of the modified copolymers were also studied as polymer-supported catalysts of model reactions such as oxidation of cyclohexene with organic hydroperoxides. The catalytic activity of the molybdenum-containing polymer complex catalyst (P4VP-MoO22+) in the principal epoxidation reaction was higher than that of the vanadium-containing (P4VP-VO2+) one, whereas, the opposite order of activities was found for the side reaction of allylic hydroxylation of cyclohexene. Under selected reaction conditions, the yields of the principal reaction products cyclohexene oxide (1,2-epoxycyclohexane) and 2-cyclohexene-1-of were 76.2% and 18.0%, respectively. (c) 2007 Elsevier Ltd. All rights reserved.