We have examined the role of the chiral amine cocatalyst in the recently discovered helix-sense-selective polymerization of a phenylacetylene using a catalytic system consisting of an achiral rhodium complex ([Rh(norbornadiene)Cl](2)) as the catalyst and a chiral amine as the cocatalyst. Several chiral amines were effective for the polymerization reaction and their effectiveness depended on their bulkmess and coordination ability to rhodium. The sense selectivity of the polymerization increased with the concentration of the chiral amines. To discuss the structure of the true active species in the catalytic system, we have synthesized a new chiral rhodium complex having two chiral amines as ligands ([Rh (norbomadiene) (chiral amine)(2)]+BF4-). The isolated chiral complex also catalyzed the helix-senses-elective polymerization. These findings suggest that a chiral rhodium complex having two chiral amines may be the true active species when using the catalytic system consisting of [Rh(norbornadiene)Cl](2) and a chiral amine. (C) 2004 Elsevier Ltd. All rights reserved.