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The interfacial behavior of novel dicephalic cationic surfactants, N,N-bis[3,3'-(trimethylammonio)propyl]alkylamide dibromides and N,N-bis[3,3'-(trimethylammonio)propyl]alkylamide dimethylsulfates, was analyzed both experimentally and theoretically in comparison to their linear standards, 3-[(trimethylammonio)propyl]dodecanamide bromide and 3-[(trimethylammonio)propyl]dodecanamide methylsulfate. Adsorption of the studied double head-single tail surfactants depends strongly upon their structure, making them less surface active in comparison to the single head-single tail structures having the same alkyl chain length. Surface tension isotherms of aqueous solutions of the studied dicephalic derivatives were measured using the pendant drop shape analysis method and interpreted with the so-called surface quasi-two-dimensional electrolyte (STDE) model of ionic surfactant adsorption. The model is based on the assumption that the surfactant ions and counterions (bromide and methylsulfate ions in the studied case) undergo nonequivalent adsorption within the Stern layer, and it allows for accounting for the formation of surfactant ion-counterion associates in the case of multivalent surfactant headgroup ions. As a result, good agreement between theory and experiment was obtained. Additionally, the presence of surfactant-counterion complexes was successfully confirmed by both measurements of the concentration of free bromide ions in solution and molecular modeling simulations. The results of the present study may prove useful in the potential application of the investigated dicephalic cationic surfactants.