The mass chromatographic fingerprints of the water extracts of Atractylodes rhizome and Atractylodes lancea rhizome were analyzed by LC-MS. Three new acylsucrose derivatives [2,6,3',6'-tetra(3-methylbutanoyl)sucrose (1), 2,4,3',6'-tetra(3-methylbutanoyl)sucrose (2), and a mixture of 3',4',6'-tris(3-methylbutanoyl)-1'-(2-methylbutanoyl)sucrose and 1',3',4',6'-tetra(3-methylbutanoyl)sucrose (6)), along with three known acylsucroses (2,6,3',4'-tetra(3-methylbutanoyl)sucrose (3), 2,4,3',4'-tetra(3-methylbutanoyl)sucrose (4) and a mixture of 2,3',6'-tris(3-methylbutanoyl)-1'-(2-methylbutanoyl)sucrose and 2,1',3',6'-tetra(3-methylbutanoyl)sucrose (5)] were isolated as the marker compounds of Atractylodes rhizome and Atractylodes lancea rhizome. The structures of the compounds were elucidated by MS/MS analyses and NMR experiments.