Anionic polyolic surfactants, alpha-sulfo fatty acids that straight long chain alkyl group has from 12 to 18 hydrocarbon numbers, was synthesized with sulfur trioxide-dioxane complex to good yields. New sodium alpha-sulfo long chain fatty acid monoglyceride were obtained by reaction that the ketalificaticn and esterification of glycerol, acetone and alpha-sulfo long chain fatty acid and hydrolysis respectively. These reaction products separated by column chromatography and their Rf values(Rf×100) were 19, 21, 24 and 26 respectively. These compounds were identified by infrared spectroscopy and 1H NMR spectroscopy.