To verify the presence of yohimbine and its four stereoisomers (corynanthine, α-yohimbine, β-yohimbine, and isorauhimbine) in health food and to perform a quantitative analysis, we examined the separation and detection conditions for each component by GC-MS and LC-UV-MS. As a result, in GC-MS analysis, baseline separation of all five components (yohimbine and its four stereoisomers) was achieved with a mid-polar column. However, the presence of a water desorption peak due to heating, calibration curves with poor linearity, and low recovery rates suggested that the use of GC-MS for quantitative analysis required further consideration. On the other hand, in LC-UV-MS analysis, baseline separation of all the five components was possible when a mixture of ammonium bicarbonate buffer and acetonitrile was used as the mobile phase. In addition, calibration curves showed adequate linearity with good recovery rates. On the basis of these results, we decided to employ the analytical condition by LC-UVMS. Using this method, we analyzed commercial health food to determine the actual contents of yohimbine and its stereoisomers, and identified food products in which only yohimbine was detected, as well as those in which yohimbine and its four stereoisomers were detected. Furthermore, we found at a high frequency food products in which corynanthine and α-yohimbine were detected at higher concentrations than yohimbine.