In order to analyze the occurrence and composition of perfluorinated compounds (PFCs), 18 topsoil samples were collected around the Huaihe River in October, 2008. Total fluoride (TF) and extractable organic fluorine (EOF) were determined using combustion ion chromatography (CIC), and PFCs were quantified by HPLC/MS-MS. Among the sixteen PFCs analyzed, eleven PFCs were detected. Concentrations of PFCs ranged from n. d. to 1.22 ng x g(-1), and perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorooctane sulfonate (PFOS) were the predominant PFCs. Concentrations of PFCs showed no significant difference, but compositions varied from soil to soil. PFCs mainly came from emissions of local small chemical plants and atmospheric dry and wet deposition. The results from mass balance analysis indicated that PFCs only accounted for 0.3% of EOF and EOF comprised 0.02% of TF. There was still a large amount of organic fluorine besides PFCs, and inorganic fluorine and non-extractable organic fluorine comprised the major portion of TF. Furthermore, the current analysis method could not detect all kinds of PFCs and related unknown organic fluorine.