Copolymerization of norbornene (NB) with methoxycarbonylnorbornene (NB-COOCH3) was carried out with catalytic system of Ni{CF3C(O)CHC[N(naphthyl)]CH3}(2) and B(C6F5)(3) in toluene. The catalytic system exhibited higher activity 2.69 x 10(5) (gpolymer/mol Ni h) for copolymerization of norbornene and methoxycarbonylnorbornene. The influence results of the comonomer feed content on the polymerization showed that the NB-COOCH3 has a very high insertion ratio in all copolymers, and the NB-COOCH3 content in copolymers can be controlled to be 7.9-77.6 mol % at content of 10-90 mol % of the NB-COOCH3 in the monomer feeds ratios. The reactivity ratios, r(NB-COOCH3) = 0.578 and r(NB) = 0.859, were determined by the Kelen-TUdOs method. Copolymers were processed by solution casting method, dry/wet phase inversion technique, and electrospinning. The films prepared by solution casting method showed good transparency in the visible region. The membranes processed by dry/wet phase inversion technique were microporous structures. The fibers diameters fabricated by electrospinning were about 3 mu m. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4425-4432, 2011