An ABA triblock copolymer of polyvinyl acetate-b-polystyrene-b-polyvinyl acetate (PVAc-PS-PVAc) was successfully synthesized with a binary system composed of polystyrene with N,N-dimethylaniline end groups (PSda) and benzophenone to initiate the polymerization of vinyl acetate under UV irradiation. The PSda was obtained by capping the living polystyrene macrodianion with p-(dimethylamino) benzaldehyde in excess. The PVA-PS-PVA could then be obtained by hydrolysis of PVAc-PS-PVAc in the sodium ethoxide benzene solution. The intermediates and desirable copolymers were characterized by GPC, IR, and H-1-NMR in detail.