In this article, novel 2,2'-bipyridyl derivatives were synthesized and the excellent bipyridyl ligands were chosen as catalyst to apply in the copolymerization of carbon monoxide (CO) and styrene (ST) to prepare polyketone. 4,4'-Dicarboxyl-2,2'-bipyridine(4,4'-dcpy) was synthesized by use of synthesized 4,4'-dimethyl-2,2'-bipyridine(4,4'-dmpy). The products (4,4'-dmpy and 4,4'-dcpy) were characterized by melting point, NMR, IR, GC-MS, and elemental analysis. The effects of different ligands and various reaction conditions incuding the usage of ligand, p-toluenesulfonic acid, solvent, p-benzoquinone, the CO pressure, and reaction temperature on catalytic activity of the copolymerization were investigated. The catalytic activity of 4,4'-dmpy, 4,4'-dcpy and 2,2'-bipyridine were compared. The results showed that the addition of the electron-donating substituent can enhance catalytic activity, with the sequence as follows: 4,4'- dimethyl-2,2'-bipyridine > 2,2'-bipyridine > 4, 4'-carboxy 2,2'- bipyridine. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 3292-3297, 2012