Novel organic-inorganic hybrids with sulfonic acid groups were prepared using random copolymers composed of vinyl sulfonate esters and vinyl trialkoxysilanes. Five vinyl sulfonate esters with different substituent groups were employed as protecting monomers for the production of the poly(vinyl sulfonic acid) component, and three vinyl trialkoxysilanes were used as cross-linkable monomers. Free radical and reversible addition-fragmentation chain transfer (RAFT) copolymerizations were performed for the production of random copolymers with two different functional groups. The selective deprotection of the sulfonate esters of the copolymers proceeded smoothly and resulted in the formation of copolymers with lithium vinyl sulfonate units and cross-linkable trialkoxysilane units. The co-condensation of the trialkoxysilane moieties in the deprotected copolymers with cross-linkers yielded transparent hybrid films that contained lithium sulfonate groups without aromatic rings or ester linkages. (C) 2013 Elsevier Ltd. All rights reserved.