Metal-free and controlled synthesis of sulfur-containing polymer is still a big challenge in

polymer chemistry. Here, we report a metal-free, living copolymerization of carbonyl sulfide

(COS) with epoxides via the cooperative catalysis of organic Lewis pairs including bases (e.g.:

phosphazene, amidine, and guanidine) and thioureas as hydrogen-bond donors, afford welldefined poly(monothiocarbonate)s with 100% alternating degree, >99% tail-to-head content, controlled molecular weights (up to 98.4 kg/mol), and narrow molecular weight distributions (1.13–1.23). The effect of the types of Lewis pairs on the copolymerization of COS with several epoxides is investigated. The turnover frequencies (TOFs) of these Lewis pairs are as high as 112 h?1 at 25 °C. Kinetic and mechanistic results suggest that the supramolecular specific recognition of thiourea to epoxide and base to COS promote the copolymerization cooperatively. This strategy provides commercially available Lewis pairs for metal-free synthesis of sulfur-containing polymers with precise structure.