A series of short chain dialkyldimethylammonium amphiphiles ([DiC(n)][X] and [DiC(n)]2[X] with n = 6, 8, or 10) has been investigated as a function of the nature of the counteranion [X] (Cl and Br- as classical references and MoO42- and WO42- as catalytic anions). Critical aggregation concentrations,(CACs) in water were determined by surface tension measurements, and the binary phase diagrams of the surfactant/water systems were established using polarized optical microscopy (POM) and small angle X-ray scattering (SAXS). The evolution of microstructures and lyotropic phases were discussed in terms of surfactant chain length and counterion effect. A cubic phase region was observed for the divalent counteranions associated with the intermediate chain length, i.e., [DiC(8)](2)[MoO4] and [DiC(8)](2)[WO4]. Finally, the fish diagrams reflecting the polyphasic microemulsion phase behavior of the water/amphiphile/oil ternary systems were established using the carbon number of mono- and dichlorinated n-alkanes as a scan variable. The amphiphile efficiency was also discussed according to the chain length and the nature of the counterions. The hydrophilic-lipophilic behavior of the amphiphiles was evaluated on the basis of the fish diagrams allowing their classification according to the Hofmeister anion sequence. The unusual behavior of [iC(8)] [C1] and [DiC(8)](2)[MO4] (M = W or Mo) is highlighted by all experiments: these compounds are clearly intermediates between hydrotropes, [DiC(6)] cation, and surfactants, [DiC(10)] cation.