Abstract The acetate, n -valerate, and n -nonanoate esters of cholesteroal, when distributed in the form of pure compounds as liquid phases on a gas chromatographic packing, exhibit anomalous log elution time−temperature relationships. Sharp changes in the elution relationship for benzene, toluene, ethylbenzene, n -octane, and n −decane are noted at or near previously reported liquid crystal or mesophase transition temperatures. The elution times increrase sharply, as much as 3.5 times, in the transition from the cholesteric mesophase to the isotropic liquid. This represents an anomalous elution time increase with increasing temperature. Near mesophase transitions, the relationship between elution time and eluant boiling point also exhibits an anomaly. Aromatic compounds exhibit shorter elution times than those for corresponding aliphatic materials of equal carbon number. When a given mesophase is supercooled, the solute elution characteristics lie on a curve which extrapolates from the data derived within the normal mesophase range. The gas chromatographic method appears to be an excellent and general determination for liquid crystal transition temperatures. The unique temperature behavior of the cholesteryl esters also gives them some importance as liquid phases in analytical gas chromatography.