Novel Sulfonium salts with non-nucleophilic anions were synthesized and applicability of these salts as initiators was demonstrated by carried out polymerization (photo and thermal) of epoxides as well as vinyl ether monomers. Newly synthesized initiators showed good activity for the photo and thermal polymerization. Synthesis, characterization, and activity of initiators have been described. (c) 2008 Wiley Periodicals, Inc.