In this paper, four type of Diethylene glycol di(α-sodium sulfonate) alkyl carboxylic ester surfactants were synthesized through esterification and sulfonation reaction from the starting materials of fatty acid, diethylene glycol and chlorosulfonic acid. The structures of the products were characterized by IR and elemental analysis. The surface activity and self-assembly behavior of the gemini surfactants aqueous solutions were investigated. The results showed that the cmc of the gemini surfactants is about 1～2 order of magnitude lower than that of the ordinary surfactant SDS. With the increase of the carbon atom number of hydrophobic alkyl chains, the surfactant exhibits much higher surface activity. The results of steady-state fluorescence quenching measurement showed that the aggregation number of the gemini surfactants decreased with the increase of the carbon atom number of hydrophobic alkyl chains.