Self-assembly of pure ester-containing cationic gemini surfactants, dodecyl esterquat, and dodecyl betainate geminis, and cation-rich catanionic mixtures of them with sodium dodecyl sulfate (SDS) were investigated using surface tension, electrical conductivity, dynamic light scattering (DLS), transmission electron microscopy (TEM) and cyclic voltammetry (CV) measurements in the absence and presence of KCl. Different physicochemical properties such as the critical micelle concentration (CMC), degree of counterion dissociation (alpha(diss)), interfacial properties, morphology of aggregates, and interparticle interaction parameters were determined. Both geminis formed micelles in the absence of KCl, and mixing with SDS did not change the morphology; just a growth in micelle size was observed. However, the aggregation behavior of these geminis with respect to the position of the ester bond in the alkyl chain appeared completely different in the presence of KCl. Esterquat gemini formed cubic nanoparticles (or cobosomes) in the presence of [KCl] = 0.05 M and transformed into spherical micelles upon increasing the surfactant concentration. By contrast, betainate gemini formed vesicles in the presence of [KCl] = 0.05 M and subsequently converted to micelles as the surfactant concentration increased. The morphology of esterquat gemini (in the presence of 0.05 M KCl) after mixing with SDS changed from cubic nanoparticles (or cobosomes) to cylindrical nanoparticles coexistent with cobosomes. Betainate gemini remained vesicular upon mixing with SDS, and no dramatic structural change of aggregates took place. The morphology changes of aggregates upon mixing with SDS were explained from calculating the interactions between two gemini surfactants and SDS on the basis of regular solution theory.