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A series of trimeric sulfonate surfactants 1,2,3‐tri(2‐oxypropylsulfonate‐3‐alkylether‐propoxy) propanes were prepared by the reaction of glycerin triglycidyl ether with long‐chain alcohols, followed by sulfonation with 1,3‐propane sultone. Glycerin triglycidyl ether was synthesized by the reaction of epichlorohydrin with glycerin. The chemical structures of the prepared compounds were confirmed by FTIR, 1H NMR and element analysis. Their solution properties were characterized by use of the method of equilibrium and dynamic surface tension, steady‐state fluorescence spectroscopy of pyrene and fluorescence quenching. With the increasing length of the carbon chain, the values of their CMC initially decreased. All these trimeric sulfonate surfactants had good water solubility. These compounds were superior in surface active properties to the reference surfactant SDS. The efficiency of adsorption at the water/air interface (pC20) of these surfactants was very high. It is found that the shorter hydrocarbon chain length of the trimeric sulfonate surfactants, the faster the rate of decrease of surface tension, and the bigger the aggregation number of the trimeric sulfonate surfactants.