In order to investigate the significance of the pairing of Radix Bupleurum (RB) and Radix Paeoniae Alba (RP),the optimal extraction conditions were determined by single-factor investigation,and the volatile components of RB,RP and RB-RP were determined by headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS),and the percentage content of each component was determined by area normalization and subjected to principal component analysis (PCA).The results showed that there were ten volatile components shared by RB,RP and RB-RP,but the contents of the shared components were different.The PCA scores of the three pairs were significantly different,with the highest PCA score for the volatile components of the pair.Most of the volatile components of the pair of RB-RP came from RB,and the combination of RB-RP produced new active ingredients,and from the volatility point of view,the combination of RB-RP has certain potency and toxicity reduction effects.