A liquid chromatograph/mass spectrometry (LC/MS) method was developed for the simultaneous quantitation of seven compounds (safflor yellow A, puerarin, daidzein, ginsenosides (Rg1, Rb1, Rd), and notoginsenoside R1) in rat plasma samples with sufficient sensitivity to facilitate analysis of samples collected after an intravenous injection of Naodesheng. The plasma samples were subjected to protein precipitation with acetone, and analyzed using negative atmospheric pressure chemical ionization mass spectrometry in selected ion monitoring (SIM) mode with baicalin as an internal standard. Good linearity for all the seven compounds was observed. The intra- and inter-day precision of analysis was <15.0% for each compound, and the accuracy ranged from 90.0% to 109.0%. This quantitation method was successfully applied to a pharmacokinetic study of following intravenous injection of rats with Naodesheng.