The aim of the present study was to examine, both experimentally and theoretically, the interfacial behavior of cleavable gemini ester quat-type cationic surfactants in comparison to a standard gemini representative. For the theoretical description of the air/water surface tension isotherms of the corresponding geminis, a modified model of multiply charged ionic surfactant adsorption (surface quasi-two-dimensional electrolyte, STDE), taking into account counter ion specificity and formation of surfactant ion-counter-ion associates, was used. As a result, good agreement between theory and experiment was obtained.