The combination of palladium complex ((Bu3P)-Bu-t)Pd(Me)Cl (1) and NaB[3,5(CF3)(2)C6H3](4) (NaBAr4) catalyzed homopolymerization of a novel monomer, norbornene (NB) with a pendent 2-fluorosulfonyltetrafluoroethoxymethyl chain (NBSF). Catalytic activities of 1/NaBAr4 were higher than those of previously reported palladium or nickel catalysts, probably, because the palladium center with electron donative (Bu3P)-Bu-t ligand was barely poisoned by the sulfonyl fluoride coordination. Thus, 1/ NaBAr4 is the current best catalyst system for NBSF polymerization. The catalyst system also gave copolymers of NB with NBSF. The obtained copolymers have high sulfonyl-fluoride incorporation and a narrow molecular weight distribution. Present catalyst system could control incorporation ratio of NBSF by changing a feed monomer ratio with slow addition of NB solution. (C) 2008 Wiley Periodicals, Inc.