Botanpi (Paeonia moutan Sims. (= P. suffruticosa Andrews)) is one of the most important crude drugs in Chinese medicine, used in prescriptions for chronic inflammatory disease and other conditions. Previous analytical studies identified compounds such as paeoniflorin but no study of its essential oils had been reported. This study deals with the isolation, identification and sensory evaluation of the major volatile components of Botanpi (with core I and without core II). GC, GC-MS, IR and NMR analyses showed that the essential oils of both types had very similar gas chromatogram patterns with slight differences. Thirty components were identified in each, with 28 being reported for the first time as Botanpi components. Paeonol was the main component, with contents of about 93.2% in I and 97.8% in II, and had a sweet, Botanpi-like aroma. Other components included furfural, 5-methyl-2-furfural, methyl benzoate, furfuryl alcohol, phenol and benzoic acid, which were more abundant in I than in II. The essential oil of II had a stronger woody and Botanpi-like odor, corresponding to its higher paeonol content.