Double chain surfactants present specific benefits in various applications, such as the enhanced oil recovery and fabric care due to their relatively high packing parameter, which leads to the easier formation of the lamellar microstructure. A series of double chain quaternary cationic ammonium surfactants and amphoteric surfactant (IKD-CAT DiC n , IKD-diquat DiC n with n = 11, 13, 15, and IKD-dibetaine DiC 15 ) have been designed and synthesized in Solvay. The physicochemical properties of these surfactants were studied in this work in order to understand their self-assembly during the applications. Critical micelle concentration and the lyotropic liquid crystals as a function of concentration was investigated with various techniques, such as surface tension-meter, polarizing optical microscopy, and small-angle X-ray scattering. In general, the hydrophilic group structure determines the aggregation evolution patterns and the specific phase concentration range depends on the hydrophobic chain length. A multilayer vesicle aggregation was formed at low concentration and only lamellar phase exists in the phase diagram for IKD-CAT. Besides the lamellar phase, the hexagonal and cubic phases were also observed in IKD-diquat solutions as the concentration was increased.