Phase diagrams of binary symmetric double-tailed alkylbenzenesulfonate surfactant/water systems, as well as the structure of the phases, were determined using crossed polars, polarized light microscopy, H-2 NMR spectroscopy, Nomarski differential interference contrast optics, and cryo-transmission electron microscopy. The isotropic phase, the lamellar phase, and a high-viscosity solution representing an intermediate between the isotropic phase and the mesophase, which refers to the beginning of the formation of vesicles, were found. As may be expected, the isotropic phases at higher concentrations are formed mostly at higher temperatures. Isotropic regions are followed by regions characterized as the isotropic solutions containing vesicles; the optically isotropic phase contains a lamellar dispersion of vesicles in solution. The viscosity of these phases is found to be high near the borderline of the two-phase regions. At the same concentrations two-phase regions were found to contain the isotropic + lamellar phases at the higher temperature and the isotropic + crystalline phase at the lower temperature. Molecular-mechanical and semiempirical quantum-mechanical calculation searches for the global minimum in the conformational space of alkylbenzenesulfonate ions were conducted to examine the influeuce of monomer molecular structure on the micellar shape.