Warfarin was converted into O-perfluoroacyl derivatives and separated into enantiomers by capillary GC with chiral stationary phase of polydimethylsiloxane anchored with S(-)-t-leucine-S(-)-1-phenylethylamide. All the derivatives showed almost complete separation. Especially in the case of O-heptafluorobutyryl derivative, baseline separation could be observed.