A method is described for the enantiomeric quantitation of some chiral compounds via online coupling of reversed-phase liquid chromatography-gas chromatography. The evaluation of some variables affecting the experimentation (i.e., the packing material used in the interface, volume of the transferred fraction, desorption time, initial temperature of the interface, and purge time) makes it possible to optimize the recoveries obtained for some chiral terpenes and lactones using a capillary column of beta-cyclodextrin dissolved in OV-1701. The proposed method allows the enantiomeric analysis of aqueous matrices obtaining relative standard deviations lower than 9% and detection limits ranging from 0.26-0.93 ppm for the investigated compounds.