We report the first example of alternating copolymerization of a polar vinyl monomer and carbon monoxide using vinyl acetate. Alternating copolymers with high molecular weights were prepared employing palladium catalysts with phosphine-sulfonate bidentate ligands. NMR and MALDI-TOF MS analyses revealed that the obtained materials were alternating copolymers of vinyl acetate and carbon monoxide. This is also the first nonradical pathway for polymer synthesis with vinyl acetate, one of the most inexpensive and readily available polar vinyl monomer, as a major component.