A series of asymmetric surfactants were prepared from cationic surfactant, hexadecyltrimethylammonium bromide, and anionic surfactant, sodium alkyl sulfate (the number of carbon atoms per chain being 10, 12, or 14). The influence of the alkyl chain asymmetry on the thermal properties of formed hexadecyltrimethylammonium alkyl sulfates was investigated by means of polarizing microscopy, differential scanning calorimetry, and X-ray diffraction. Asymmetric catanionic surfactants exhibited a complex polymorphism and thermotropic mesomorphism from the stable crystalline form to the isotropic phase. On heating, successive phase transitions (several solid crystalline-solid crystalline, solid crystalline-liquid crystalline, and liquid crystalline-isotropic liquid) were observed. The number of polymorphs, in all of the bilayered structure, depended on the asymmetry between the lengths of surfactant tails. The basic lamellar thickness varied linearly with the increase of alkyl sulfate chain length. An increase of the basic lamellar thickness with temperature was determined. Polarizing microscopy revealed a characteristic texture of the smectic phase. On cooling, all compounds underwent reversibly the isotropic liquid-liquid crystalline transitions, while crystallization from melted samples was kinetically controlled,