Abstract: OBJECTIVE To establish an HPLC method for determination of 5 kinds of chemical constituents in Paeoniae Radix Alba. Comprehensively evaluate the quality of different grades of Radix Paeoniae Alba, and provide a reference for the research on the commercial specification grade standard of Radix Paeoniae Alba. METHODS The HPLC were performed on a SunFire^® C₁₈ column(4.6 mm×250 mm, 5 µm) with the gradient elution of acetonitrile(A)-0.05% phosphoric acid aqueous(B). An external standard method was established for simultaneous determination of 5 chemical components in Radix Paeoniae Alba, including gallic acid, albiflorin, paeoniflorin, 1,2,3,4,6-penta-O-galloyl-β-D-glucose(β-PGG) and benzoylpaeoniflorin. A principal component analysis(PCA)-cluster analysis(CA) model was used for multivariate statistical analysis. RESULTS The average contents of 5 components in 5 grades of Paeoniae Radix Alba slices samples(first-rate-quality product, second-rate-quality product, third-rate-quality product, gradeless and uniformly-priced goods and fresh cut pieces) were as follows: gallic acid(1.000 9, 1.016 4, 0.949 6, 1.039 7, 0.974 7 mg·g^-1), albiflorin(5.000 6, 5.336 6, 6.124 0, 5.449 8, 9.922 2 mg·g^-1), paeoniflorin(30.212 9, 29.478 3, 30.186 7, 29.516 6, 35.251 1 mg·g^-1), β-PGG(3.250 3, 2.498 1, 3.704 9, 3.736 9, 3.710 0 mg·g^-1) and benzoylpaeoniflorin(0.651 8, 0.754 7, 0.782 0, 0.711 3, 0.748 9 mg·g^-1), respectively. The results of PCA showed that the fresh cut pieces were relatively better, but the scores of other grades did not reflect the positive correlation with itself level. The results of CA showed that the samples were divided into 5 categories while the judging distance was<5, and the 11 batches of fresh cut slices were clustered into a single category and other levels interact into 4 categories. CONCLUSION The method has good repeatability, accuracy and recovery. Using the 5 component content as indexes to evaluate the quality of different Paeoniae Radix Alba slices samples based on PCA-CA can provide the reference for the products of standard specifications of commodities of Paeoniae Radix Alba.