The development of new or more sustainable, active, efficient, controlled, and selective polymerization reactions or processes continues to be crucial for the synthesis of important polymers or materials with specific structures or functions. In this context, the newly emerged polymerization technique enabled by main-group Lewis pairs (LPs), termed as Lewis pair polymerization (LPP), exploits the synergy and cooperativity between the Lewis acid (LA) and Lewis base (LB) sites of LPs, which can be employed as frustrated Lewis pairs (FLPs), interacting LPs (ILPs), or classical Lewis adducts (CLAs), to effect cooperative monomer activation as well as chain initiation, propagation, termination, and transfer events. Through balancing the Lewis acidity, Lewis basicity, and steric effects of LPs, LPP has shown several unique advantages or intriguing opportunities compared to other polymerization techniques and demonstrated its broad polar monomer scope, high activity, control or livingness, and complete chemo- or regioselectivity, as well as its unique application in materials chemistry. These advances made in LPP are comprehensively reviewed, with the scope of monomers focusing on heteroatom-containing polar monomers, while the polymerizations mediated by main-group LAs and LBs separately that are most relevant to the LPP are also highlighted or updated. Examples of applying the principles of the LPP and LP chemistry as a new platform for advancing materials chemistry are highlighted, and currently unmet challenges in the field of the LPP, and thus the suggested corresponding future research directions, are also presented.