A series of novel gemini surfactants, namely phenyl-1,4-bis [(carbamoylmethyl) N,N-dimethylalkyl ammonium chloride)] (a, b and c) were synthesized systematically and characterized by FT IR, 1 H NMR, 13 C NMR and MS. Their surface and bulk properties were evaluated by surface tension, conductivity, viscosity, dynamic light scattering (DLS) and transmission electron microscopy (TEM) measurements. These surfactants have been found to have low surface tension (γ γ γ γCMC) values as compared to other categories of gemini cationic surfactants and to form vesicles in solution at low concentration. The DLS and TEM studies showed that the aggregations of the above surfactants changed from larger globule vesicles and smaller globule micelles to network aggregates and then to globule vesicles with the increase of the surfactant concentration. It is assumed that this unusual aggregation behavior is related to the transformation of molecular conformation, phenyl-1,4-bis(carbamoylmethyl) spacer with rigidity and a hydrogen-bonding capability. The thermodynamic parameters of micellization process, namely, standard Gibbs free energy (∆Gºm), enthalpy (∆Hºm) and entropy (∆Sºm) were derived from conductivity measurement at different temperatures. Krafft points of three gemini surfactants are very low.Gemini surfactants are amphiphilic molecules containing two hydrophilic head groups and two hydrophobic tails connected by a spacer at two head groups. Many studies have been carried out on gemini surfactants, focusing on their unique surface and bulk properties such as high surface activity, low critical micelle concentration(CMC), and more abundant self-assembly morphologies than the corresponding traditional single-chain surfactants. 1-4 Owing to these unique properties, gemini surfactants have been widely used in industrial detergency, the construction of high-porosity materials, templates for the synthesis of nanoparticles, nanorods, etc. 5-10 So, aggregation behavior of surfactants attract great attention in academic research. The chemical structures of the gemini surfactants play an important role in their aggregation behavior. 11, 12 Especially, the nature of the spacer group (length, flexibility, polarity) has been shown to be of the utmost importance in determining the solution properties of aqueous gemini surfactants. 13, 14 These effects lead to the synergism of two alkyl tails of a gemini molecule, the change in the charge density of its headgroup, the variation of its molecule geometry by which rich structures and morphologies of aggregates yield, etc. More detailed, the flexible spacer influences the above functions of the gemini mainly depending on its length. 6,15 Too long flexible spacer can bend toward the alkyl tails so as to meet the chemical environment around the molecule, by which the molecule self-assembly is influenced. The effect of the short rigid spacer is almost identical with that of the flexible spacer having a similar length. 16 However, the long rigid spacer yields quite different effects from the flex...