A selective pressurized liquid extraction and gas chromatography coupled with triple quadrupole mass spectrometer method was developed for simultaneous determination of 52 pesticide residues in medicine and food dual-purpose herbs. The developed extraction method integrated extraction and cleanup processes for sample preparation. The sorbents, 5 g Florisil and 100 mg graphitized carbon black, were placed inside the extraction cell to remove matrix interferences. Optimized conditions of selective pressurized liquid extraction were ethyl acetate as extraction solvent, 120°C of extraction temperature, 6 min of static extraction time, 50% of flush volume extracted for two cycles. An ultra inert capillary GC-MS HP-5 UI column (20 m × 0.18 mm id, 0.18 μm) and column backflush system were used for the analysis. Multiple-reaction monitoring was employed for the quantitative analysis with electron ionization mode. All calibration curves showed good linearity (r2 > 0.995) within the test ranges. The average recoveries of most pesticides were from 81 to 118%. The validated method was successfully applied for the determination of pesticide residues in four herbs. The results indicate that selective pressurized liquid extraction and GC-MS/MS is a sensitive and reliable analytical method for the simultaneous determination of multiple pesticide residues in herbs. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.