A high performance liquid chromatography coupled with electro spray ionization tandem mass spectrometric（HPLC-ESI MSn） method was developed for the simultaneous determination of psoralen and bergapten in aqueous extraction from Radix fici hirtae.The separation of psoralen and bergapten was performed on a Hypersil C18 column（150 mm×4.6 mm,5 μm）,using water-methanol（50∶50）as mobile phase at a flow rate of 0.80 mL·min-1.The detection was carried out at room temperature with a detection wavelength of 300 nm（PDA） and an injection volume of 10 μL.The influencing factors for liquid-liquid microextraction（LLME） were investigated.Under the optimized conditions,the calibration curves were linear in the range of 0.55-2 200 μg·L-1 for psoralen and 1.00-4 000 μg·L-1 for bergapten,with correlation coefficients of 0.999 9 and 0.999 2,respectively.The limits of detection（S/N=3） were 0.13 μg·L-1 and 0.18 μg·L-1，and the limits of quantitation（S/N=10） were 0.43 μg·L-1 and 0.60 μg·L-1, respectively.The relative standard deviations（RSDs,n=5） of 110 μg·L-1 psoralen and 100 μg·L-1 bergapten were both less than 1%.The recoveries of psoralen and bergapten were 100% and 101%,respectively.The results demonstrated that LLME combined with LC-MS was a rapid,convenient and efficient method for the determination of herbal compositions,and could provide the basis for the quantitation detection of psoralen and bergapten in aqueous sample from Radix fici hirtae.