The application of complexation gas chromatography in contemporary enantiomer analysis was investigated. Enantiomers were separated without derivatization on Chirametal stationary phases, such as manganese(II), cobalt(II) and nickel(II) bis[3-(heptafluorobutanoyl)-(1 R)-camphorate], coated on high-resolution glass and fused-silica open-tubular columns. Enantiomeric excesses (ee) up to 99.9% can be precisely determined by complexation gas chromatography. Employing the gas chromatography-mass spectrometry (single ion monitoring) technique, the determination of ee and absolute configurations of solutes, present in complex mixtures, can be performed at the low picogram level. For the first time, pertinent sources of error in the gas chromatographic determination of ee were identified and novel experimental verifications thereof are presented. Interconversion profiles due to inversion of configuration during enantiomer separation by complexation gas chromatography have been detected. Inconsistencies of an empirical quadrant rule, correlating absolute configuration and order of elution of cyclic ethers from nickel(II) bis[3-(heptafluorobutanoyl)-(1 R)-camphorate], are reported.