The invention relates to a method for carrying out anionic addition polymerization on a polar vinyl monomer. The method comprises the following steps: firstly, reducing water in all the adopted reagents to be less than 10ppm, then adding a reactive species, diphenylethylene or triphenyl diethylene, excess K-O-Ar, at least one polar vinyl monomer and/or at least one non-polar vinyl monomer into an organic solvent, and carrying out reaction between the room temperature and the temperature of 60 DEG C to realize anionic addition polymerization. The Li countra-ions in the reactive species can be converted into the K countra-ions due to the adoption of excess K-O-Ar, the side reaction during anionic polymerization of the polar vinyl monomer can be inhibited effectively due to the adoption of the inactive Li-O-Ar, and the anionic polymerization can be carried out between the room temperature and the temperature of 60 DEG C. The method provided by the invention is used for carrying out anionic polymerization on widely used monomers on a feasible industrial level to generate abundant segmented, telechelic, branched and star-shaped high-performance polymers in complex structures.