The hyperbranched polyglycerol analog, hyperbranched poly[glycerol‐co‐3‐methyl‐3‐(hydroxymethyl)oxetane] [HP(G‐co‐M)], was synthesized in one‐step by random copolymerization of glycidol and 3‐methyl‐3‐(hydroxymethyl)oxetane (MHO). The obtained polymer exhibited a thermoresponsive behavior in an aqueous solution, and the corresponding lower critical solution temperature (LCST) could be readily adjusted by changing the feed ratio of glycidol to MHO. The MTT assay against COS‐7 cells demonstrated that HP(G‐co‐M) had low cytotoxicity. Moreover, the existence of numerous hydroxyl terminals of HP(G‐co‐M) facilitated their further modification and functionalization. All of these characteristics suggest that this novel backbone‐thermoresponsive hyperbranched polyglycerol is a promising functional material for biomedical applications.
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