RTILs are organic salts with melting points under 100ºC. These materials are of strong interest in green chemistry as well as for electrochemical applications. The bis((trifluoromethyl)sulfonyl) imide ion is one of the favored anions for RTILs. Our interest has been in new methods for the synthesis of ionic liquids with this anion and extensions to other related bis((perfluoroalkyl)-sulfonyl)imides. Several interesting ionic liquids have been synthesized containing difunctional sulfonimide anions and joined with symmetric and asymmetric imidazolium cations. Propyl and heptyl di-imidazolium cations were also combined with difunctional sulfonimide cations. TGA for these RTILs show good stability with decomposition onset temperatures above 370ºC. DSC spectra illustrate low melting points for RTILs with symmetric cations, and only glass transition type phase changes for those with asymmetric cations. These interesting properties and methodologies have been pursued into trifluorovinyl ether (TFVE) monomer syntheses because of the TFVE moiety's ability to undergo thermal polymerization. These novel examples of ionic liquids utilizing polyfunctional sulfonimide anions will be presented.