Branched alkylbenzenesulfonate gemini surfactants: sodium 6,6'-(propane-1,3-diylbis(oxy))bis(3-(2-propylpentyl)benzenesulfonate) (C8BC3C8B), sodium 6,6'-(propane-1,3-diylbis(oxy))bis(3-(3,5,5-trimethylhexyl)benzenesulfonate) (C9BC3C9B), and sodium 6,6'-(propane-1,3-diylbis(oxy))bis(3-(2,4, 4-trimethylpentan-2-yl)benzenesulfonate) (T-C8BC3C8B) have been synthesized. Their interfacial activity and aggregation behavior in aqueous solution were studied by surface/interface tension measurement, electrical conductivity, isothermal titration microcalorimetry, (1)H NMR spectroscopy, dynamic light scattering, steady-state fluorescence and cryogenic transmission electron microscopy. The critical aggregation concentration (CAC) and the minimum average surface area/molecule (A(min)) decrease with the decrease of the branching factor, i.e., in the order of T-C8BC3C8B, C8BC3C8B and C9BC3C9B. Moreover, alkyl side chain branches generate much more significant increases in CAC and A(min) for the gemini surfactants than single-chain surfactants. However, the branching factor does not change the air/water surface tension at CAC regularly. Instead, the air/water surface tension decreases with the increase of the carbon number of the hydrocarbon chains. In addition, it is noted that the branched gemini surfactants display high efficiency in reducing toluene/water interfacial tension. Interestingly, the increase in the branching factor leads to much more endothermic enthalpy of aggregation. All these three surfactants form spherical vesicles in aqueous solution and may present a parallel-displaced structure with a directional arrangement of the benzene ring in the vesicles. (C) 2011 Elsevier Inc. All rights reserved.