The gas chromatographic performance of differently derivatized a-, p-, and y-cyclodextrins in the separation of racemic mixtures of volatile is investigated. The performances of 2,3,6-permethylated a-, p-, and y-cyclodextrins and 2,6-dimethyl-3-trifluoro-acetyl a-, p-, and y-cyclodextrins mixed with different ratios of OV-1701 or OV-1701-OH terminated were tested with racemates with widely differing structures. The influence of the percentage of cyclodextrins in polysiloxane, of film thickness of the stationary phase, of the length of the column, of column conditioning, and of the operating temperatures in the separations of different racemates has been evaluated.