Three novel rhodium complexes, with l -tyrosine ( l -Tyr), l -arginine ( l -Arg), or 2,4-diamino-6-phenyl-1,3,5-triazine (Dpt) as a ligand, named as [Rh(cod)( l -Tyr)], [Rh(cod)( l -Arg)], and [Rh(cod)(Dpt) 2 ], respectively, had been synthesized for catalyzing the polymerization of phenylacetylene. Their yields were 62.34, 54.87, and 58.21%, respectively, by the most suitable synthesis conditions at 25°C for 4 h. The structures and purity of these complexes were proved by 1 H NMR, element analysis, and scanning electron microscope (SEM). It has been examined that phenylacetylene could be polymerized by the three complexes as catalysts with high degrees of polymerization ( n = 368, 385, and 664, respectively) and yields (about 87.62, 88.39, and 59.67%, respectively). In conclusion, compared with traditional [Rh–N] type catalysts, the novel [N–Rh–N] type catalyst ([Rh(cod)(Dpt) 2 ]) gained better catalytic performance. By comparing the yield, Mw, and degree of their polymerization, the polymerization mechanism was found under the [N–Rh–N] type rhodium catalyst system.