The globally increasing demands for polymer materials stimulate the significantly intense attention focused on the Lewis pair polymerization (LPP) of various polar vinyl monomers catalyzed by Lewis pairs (LPs) composed of Lewis acid (LA) and Lewis base (LB). According to the degree of interaction between LA and LB, LPs could be divided into classical Lewis adduct (CLA), interacting Lewis pair (ILP) and frustrated Lewis pair (FLP). Regulation of the Lewis basicity, Lewis acidity, and steric effects of these LPs has a significant impact on the polymer chain initiation, propagation and termination as well as chain transfer reaction during polymerization. Compared with other polymerization strategies, LPP has shown several unique advantages towards the polymerization of polar vinyl monomers such as high activity, control or livingness, mild conditions, and complete chemo- or regioselectivity. We will comprehensively review the recent advances achieved in the LPP of polar vinyl monomers according to the classification of the employed LPs based on different LAs, by highlighting the key polymerization results, polymerization mechanisms as well as the currently unmet challenges and the future research directions of LPP chemistry.