Divinyl ether monomers containing phosphorous residues were synthesized by the addition reaction of glycidyl vinyl ether (GVE) with various phosphonic dichlorides or dichlorophosphates with quaternary onium salts as catalysts. The reaction of GVE with phenylphosphonic dichloride gave bis[1-(chloromethyl)-2-(vinyloxy)ethyl]phenylphosphonate (1a) in a 77% yield. The polycondensation of la with terephthalic acid was also carried out with 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) as a condensing agent to afford the corresponding phosphorus-containing polyester. A multifunctional monomer containing both vinyl ether groups and methacrylate groups was prepared by the reaction of la with methacrylic acid with DBU. The photoinitiated cationic polymerization of these vinyl ether compounds proceeded rapidly with his [4-(diphenylsulfonio)phenyl]sulfide-bishexafluorophosphate as the cationic photoinitiator without a solvent upon ultraviolet irradiation. (C) 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2031-2042, 2004.