A simple, efficient, and rapid method is described for separation of the enantiomers of propoxyphene by capillary electrophoresis with neutral cyclodextrins as chiral separators. This method has several advantages over the crystallization method employed by some forensic laboratories, including unambiguous results, ease of use, and smaller sample-size requirement. The method enables baseline separation of the propoxyphene enantiomers in approximately six minutes, which is less than one-third of the time required for a previously published method.