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The pharmacokinetic study of DSS, PCA and their related metabolites HLMA and PAA in Chinese healthy volunteers after oral administration of CDDPDevelopment of an LC-MS/MS method for simultaneous determination of DSS,PCA,HMLA and PAA.Application of the LC-MS/MS method for determination of the four analytes in human plasma.The first pharmacokinetics study of the four analytes in human after oral administration of Compound Danshen Dripping Pills(CDDP).Compound Danshen Dripping Pills (CDDP), a herbal patent medicine, is widely used in China for the prevention and treatment of cardiovascular diseases. A simple, sensitive and reliable method for simultaneous determination of danshensu (DSS), protocatechuic aldehyde (PCA), and their related metabolites, 4-hydroxy-3-methyloxyphenyl lactic acid (HMLA) and protocatechuic acid (PAA) in human plasma was developed and validated based on liquid chromatography tandem mass spectrometry (LC–MS/MS). The analytes and internal standard (IS), vanillic acid (VAA), were extracted from plasma with ethyl acetate and separated on a C18 column by using the mobile phase consisted of methanol-0.1% formic acid via gradient elution. The electrospray ionization (ESI) source was applied and operated under the multiple reaction monitoring (MRM) mode. The linear calibration curves were obtained at the concentration ranges of 0.46–1000 ng/mL for DSS and PAA, and 1.38–1000 ng/mL for PCA and HMLA, respectively. The inter- and intra-day precisions (RSD%) were less than 13.5%, and the accuracy (±RE%) was within 13.4%. The described method was successfully applied for the clinical pharmacokinetics of CDDP in Chinese healthy volunteers.