Small-angle neutron scattering and surface tension have been used to characterize a class of surfactants (SURFs), including, surfactant ionic liquids (SAILs). These SURFs and SAILs are based on organic surfactant anions (single tail dodecyl sulfate, DS, double chain aerosol-OT, AOT, and the trichain, TC) with substituted quaternary ammonium cations. This class of surfactants can be obtained by straightforward chemistry, being cheaper and more environmentally benign than standard cationic SAILs. A surprising aspect of the results is that, broadly speaking, the physicochemical properties of these SURFs and SAILs are dominated by the nature of the surfactant anion and that the chemical structure of the added cation plays only a secondary role.