Polymerization of several ring-substituted phenylacetylenes, i.e. p-methoxy-, p-methyl-, p-chloro-, and p-methoxycarbonylphenylacetylenes by the [(nbd)RhCl](2)/Ph2C=CPhLi/Ph3P ternary catalyst proceeded in a living fashion to quantitatively provide polymers with low polydispersity indices (M-w/(M)n 1.04-1.18). The initiation efficiencies were virtually quantitative. Block copolymerizations proceeded regardless of the combinations and addition orders of these monomers to selectively form the corresponding block copolymers.