In this study, a rapid chiral separation of 12 cathinones analogs has been developed and validated using cyclodextrin-assisted CE with UV and TOF-MS detection. Optimum separation was obtained on a 57.5 cm x 50 mu m capillary using a buffer system consisting of 10 mM beta-cyclodextrin (beta-CD) in a 100 mM phosphate buffer for CE-UV, and 0.6% v/v highly sulfated-gamma-cyclodextrin (HS-gamma-CD) in a 50 mM phosphate buffer for CE-MS. In the CE-MS experiment, a partial filling technique was employed to ensure that a minimum amount of cyclodextrin entered the mass spectrometer. All analytes were separated within 18 min in the CE-UV separation and identified by TOF-MS. Ten compounds were enantiomerically separated using beta-CD in the UV mode and an additional two more were enantiomerically separated using HS-gamma-CD in the MS mode. Detection limits down to 1.0 ng/mL were obtained. The method was then applied to examine seized drugs.