Impurity profiles of rifaximin produced in China were investigated systematically by LCMS methods. Eleven impurities from the raw materials of rifaximin produced in China were detected. We adopted the Diagnostic fragment-ion-based extension strategy (DFIBES) for deducing the structure of unknown impurities. Impurity 1 was the 30-hydroxylated product of rifaximin. Impurity 2 was the 25-deacetyled rifaximin. Impurity 6 was the isomeride of rifaximin. Impurity 9 was rifamycin-O.