Polymers are produced by direct photolysis of substituted aryl cyclic sulfonium Zwitterionic salts in solution or film. Analysis of zwitterionic monomers via C-13 NMR, UV, and IR spectroscopy as well as X-ray diffraction clearly identifies the structures taking part, in the photoinduced polymerization in the solid crystalline films. The protonated form of the zwitterionic monomers, however, fails to produce detectable amounts of polymer upon photolysis under any conditions. (C) 2001 John Wiley & Sons, Inc.