A series of anionic sulfonate gemini surfactants with the general structure of [(CnH2n+1)(C3H6SO3-) NCsN(C3H6SO3-)(CnH2n+1)]center dot 2Na(+) have been synthesized. While the spacer group C-s represents p-xylyl or(CH2)(3), the surfactants are abbreviated as CnCpxCn(SO3)(2) (n = 8, 10, 12) or C12C3C12(SO3)(2) (n = 12), respectively. A corresponding monomeric surfactant C12H25N(CH3)(C3H6SO3-)center dot Na+(C12NSO3) has also been prepared. The aggregation behavior of these surfactants has been studied at pH 9.2 and ionic strength of 30 mM. The gemini surfactants exhibit stronger aggregation tendencies and much less endothermic enthalpy changes of micellization (Delta H-mic) compared with the monomeric surfactant. The critical micelle concentrations (CMC) of the gemini surfactants decrease with the increase of the hydrophobic chain length from C8CpxC8(SO3)(2) to C10CpxC10(SO3)(2) but the CMC values of C10CpxC10(SO3)(2) and C12CpxC12(SO3)(2) are very close. The Delta H-mic values vary from endothermic for C8CpxC8(SO3)(2) to almost zero for C12CpxC12(SO3)(2). Besides, vesicles are observed above the CMC for all these surfactants. The water-mediated intermolecular hydrogen bonding between the tertiary nitrogen groups may assist C12NSO3 and C12C3C12(SO3)(2) in their vesicle formation, while the pi-pi interaction between aromatic rings should be another additional driving force for the vesicle formation of CnCpxCn(SO3)(2). Meanwhile, the hydrogen bonding, pi-pi interaction, and strong hydrophobic interaction provide the possibility of a multilayer formation for C12CpxC12(SO3)(2) and C12C3C12(SO3)(2) at the air/water inter-face, which is a possible reason for the extremely small minimum area occupied per surfactant molecule at the air/water interface for these two gemini surfactants. (C) 2007 Elsevier Inc. All rights reserved.