Abstract: A method for the determination of homologues of n-alkylbenzenesulfonates in whole blood by high-performance liquid chromatography (HPLC) was proposed.The sample of whole blood was diluted with an acidic extractant and purified on the Bakerbond C18 SPE column.The column was first rinsed with a mixed solution of CH3OH+HOAc+H2O (49+2+49) and then eluted with mixed solution of CH3OH and aqueous ammonia (98+2).The homologues of n-ABS were separated on Wakopak WS AS-Aqua column (250 mm×4.6 mm,5 μm) with mixed solution of acetonitrile and water (60+40) as mobile phase,and determined with UV-detection at 228 nm.Linearity ranges for 5 C10~C14 homologues of n-ABS was found ranged from 10.0 to 100.0 ng·g-1 and values of recovery of the 5 homologues in whole blood ranged from 78% to 107% were obtained.Values of intraday and interday RSD′s (n=5) were less than 10% and 13%,respectively.