α-sulfonated fatty acid polyethylene glycol esters with polyethylene oxide(addition, 3, 5, 10mol) were synthesized through esterification of α-sulfonated fatty acid methyl esters with alkyl chain length C12~C18. Their compounds were separated with column chromatography, and confirmed by TLC. Quantitative analysis of all the sulfonates were performed according to JIS K-3362 method, and ethylene oxide unit number were determined by ISO 2270 method. Structural properties of α-sulfonated fatty acid methyl esters and their derivatives were also identified from IR, and 1H NMR spectra.