Lewis pair cooperation provides a facile approach for polymerizing dissymmetric divinyl polar monomers such as 4-vinylbenzyl methacrylate in excellent regioselectivity and high reactivity at mild conditions, affording soluble polymers bearing pendant active vinyl groups with high molecular weight (up to 6.4 × 105 g/mol) and narrow polydispersity (PDI < 1.5). ESI-TOF MS study demonstrated that the polymerization process only concerned the methacrylic double bond and selectively remained the pendant allylic or styrene C═C bond.