A simple and sensitive method based on hollow fiber liquid phase microextraction（HF-LPME） was developed to separate， purify and enrich ephedrine and pseudoephedrine in human urine sample.With HF-LPME device，the extraction conditions were optimized.Under the optimal conditions using n-octyl alcohol as organic phase impregnated in the pores of hollow fiber，and acidic microliter solution（pH 2.0）as acceptor phase，the enrichment factors of 180 for ephedrine and 220 for pseudoephedrine were obtained at room temperature with extraction time of 60 min.The calibration curves- were linear in the ranges of 0.01-5 mg/L and 0.005-0.75 mg/L for ephedrine and pseudoephedrine,with their correlation coefficients of 0.998 2 and 0.997 8，respectively.The limits of quantitation（S/N=10） were 0.01 mg/L and 0.005 mg/L，respectively.With the advantages of low organic solvent consumption and high extraction efficiency， the method was suitable for the simultaneous determination of ephedrine and pseudoephedrine in urine sample.