Yuncheng basin is an area contaminated by arsenic (As). The species of As present in the study area need to be better characterized. In this study, species of As in sediment was investigated using sequential extraction method. Ion Chromatography – Hydride Generation – Atomic fluorescence Spectrometry (IC-HG-AFS) was used to determine the species of As in aquifer sediments and surrounding shallow groundwater. The instrumental system of ion chromatography(IC) couples with HG-AFS proved to be an effective method for analysis of the total As and the As speciation in sediments.