Four vinyl sulfonate ester derivatives, methyl ethenesulfonate (MES), ethyl ethenesulfonate (EES), 2,2,2-trifluoroethyl ethenesulfonate (TFES), and 2,2,2-trichloroethyl ethenesulfonate (TCLES), which are protected forms of vinyl sulfonic acids, were polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Polymers having relatively narrow molecular weight distributions and pre-determined molecular weights were obtained by the polymerization of all monomers using a suitable xanthate-type chain transfer agent (CTA). The RAFT polymerizations of EES and TCLES were found to proceed in controlled fashions under suitable conditions, as confirmed by the formation of narrow polydispersity products, molecular weights controlled by the monomer/chain transfer agent ratio, and linear increases in molecular weight with conversion. Deprotection of the ethyl group of poly(EES) by LiBr in refluxing 2-butanone proceeded smoothly to give water-soluble poly(lithium vinyl sulfonate). Poly(potassium vinyl sulfonate) was also obtained by the deprotection of poly(TCLES) using potassium tert-butoxide. The syntheses of thermoresponsive block copolymers involving poly(lithium vinyl sulfonate) segments were conducted by RAFT polymerization of N-isopropylacrylamide using poly(EES) macro-CTA, followed by deprotection. The thermally-induced phase separation behavior and assembled structures of the block copolymers were also studied in aqueous solution. (C) 2012 Elsevier Ltd. All rights reserved.