In this article, we propose very simple procedures to analyze two important indole alkaloids, reserpine and yohimbine, in Rauvolfia yunnanensis. A nonaqueous CE method has been employed using berberine as an internal standard. Optimum separation conditions were obtained when the sample was injected by pressure for 3 s at 50 mbar and then separated with the buffer containing 40 mM ammonium acetate, 2.0% (v/v) acetic acid, and 20% (v/v) acetonitrile in methanol medium at an applied voltage of 25 kV. The analytes were detected at 220 nm. The two alkaloids can be separated within 15 min and quantified with high sensitivity. Good recoveries were obtained with both the procedures, using an internal standard. Finally, these procedures were applied to the analysis of two alkaloids in Rauvolfia yunnanensis.