Utilization of palladium catalysts bearing a P-chiral phosphine-sulfonate ligand enabled asymmetric copolymerization of vinyl acetate with carbon monoxide. The obtained gamma-polyketones have head-to-tail and isotactic polymer structures. The origin of the regio- and stereoregularities was elucidated by stoichiometric reactions of acylpalladium complexes with vinyl acetate. The present report for the first time demonstrates successful asymmetric coordination-insertion (co)polymerization of vinyl acetate.