“…The constant pursuing of new polymer synthetic methodology plays a vital role in the advances of polymer materials. Multicomponent polymerizations (MCPs), as a burgeoning field in polymer chemistry, have gained wide popularity recently among polymer scientists. − Besides the advantages inherited from small molecular multicomponent reactions, such as high atom/step economy, simple and inexpensive reactants, environmental benefits, synthetic efficiency, and operational simplicity, − the unique feature of MCPs compared with other polymerizations is the great structural diversity of the polymer products that could be achieved through various combinations of multiple monomers. − Most importantly, unlike other polymerizations that only link functional monomeric units together in a polymer chain, MCPs could often build new functional units embedded in the polymer mainchain directly from the polymerizations. , With these features, MCPs could serve as a powerful tool for the construction of libraries of functional polymer materials with great synthetic simplicity and efficiency. For example, Li et al and Meier et al have reported the Passerini three-component polymerizations and Ugi four-component polymerizaitons for the synthesis of linear and hyperbranched poly(ester–amide)s/polyamides, respectively; − Tang et al have reported the A 3 -polycoupling of alkynes, amines, and aldehydes for the synthesis of polyamines; Choi et al and we have also reported a series of Cu(I)-catalyzed room temperature MCPs based on alkynes and sulfonyl azides, respectively, producing heteroatom-rich poly( N -sulfonylamidine)s with high yields and high molecular weights ( M w s), releasing N 2 as the only byproduct. − Most recently, we’ve reported the catalyst-free MCPs of elemental sulfur, diamines, and diynes/diisocyanides to directly convert elemental sulfur to sulfur-containing functional polythioamides/polythioureas with well-defined structures and good solubility under mild conditions. , …”