Hexaalkylguanidinium and 2-(dialkylamino)-1,3-dimethylimidazolinium trimethyldifluorosiliconates, precursors for two stable hexaalkylguanidinium perfluoroalkoxides, were synthesized by treating commercially available bis(dialkylamino)difluoromethane derivatives with (dialkylamino)trimethylsilanes in aprotic media. With hexamethylguanidinium pentafluoroethoxide the introduction of the lipophilic and electronegative C2F5O group was straightforwardly achieved in the case of primary and secondary alkyl triflates to furnish the respective fluorinated ethers. The molecular structures of [(CH2NMe)(2)C(NEt2)](+)[Me3SiF2](-) and [C(NMe2)(3)]F-+(-).6CH(2)Cl(2) were determined, showing in the latter case a fluoride anion octahedrally coordinated by six methylene chloride molecules via hydrogen bridges with a F...H distance of 205 pm (C...F distance 270.0(3) pm).