Objective:Rauvolfia cambodianahas been used as a Vietnamese folk medicine to treat high blood pressure and for sedation and memory loss diseases. However, to date, there have been few studies on the chemical constituents and biological activity of this medicinal plant. This study aimed to find the chemical constituents of R cambodianaand evaluate their enhancement memory properties. Methods:The aerial parts of R cambodianawere powdered and ultrasonically extracted with methanol. The methanol extract was suspended in water and successively partitioned with dichloromethane and ethyl acetate to give dichloromethane, ethyl acetate, and water-soluble extracts. Each extract was fractionated and purified by column and HPLC chromatographic methods. The chemical structures of the isolated compounds were elucidated by analysis of HRESIMS, 1D and 2D NMR spectra, and experimental and TD-DFT calculated ECD spectra. The enhancement memory property of the compounds was evaluated by their in vitro acetylcholinesterase inhibitory activity. Results:Five alkaloids (1-5) and 2 iridoids (6and 7), including one new one named rauvolcambonine (1), and 6 known compounds, perakine (2), ajmaline (3), 10-hydroxy-16-epi-affinine (4), sitsirikine (5), loganic acid (6), and secoxyloganin (7) were isolated and identified from the aerial parts of R cambodiana. Compounds 4and 5significantly showed acetylcholinesterase inhibitory effects in vitro with IC50values of 30.1 ± 1.4 µM and 65.5 ± 3.3 µM, respectively. The other compounds inhibited acetylcholinesterase with IC50values ranging from 111.0 ± 6.0 µM to 197.6 ± 19.8 µM. Conclusion:One new (1) and 3 other compounds (2, 4-7) were recorded from R cambodianafor the first time. The NMR spectroscopic data of compound 4are reported herein for the first time. Our study preliminarily revealed that the vobasenal framework type alkaloids could be active ingredients of Rauvolfiaspecies and responsibility for the enhancement memory property of these plants.