Two new bis(perfluoroalkyl)arylsulfonyl imide monomers, which contain the aryl diazonium moiety and intramolecular zwitterionic fragment, have been designed and prepared for the first time from perfluoro(3-oxa-4-pentene)sulfonyl fluoride. As promising monomer candidates for high-performance proton exchange membrane fuel cell electrolytes, these two monomers have furnished perfluorinated electrolytes that include the polymers from perfluorinated sulfonic acid or perfluorinated sulfonimide monomers. The synthesis strategies and NMR analysis are summarized and discussed in details.