For the first time, four commercial ionic liquid columns (SLB-IL59, SLB-IL76, SLB-IL82 and SLB-IL100) for gas chromatography have been comprehensively evaluated in terms of efficiency, polarity and solvation properties. Grob tests and McReynolds constants showed that they were all high-efficiency columns of high polarity, but with low inertness to compounds with hydrogen bonding capabilities. The solvation parameter model was used to characterize the solvation interactions of the four columns in the 80-160°C temperature range. Results revealed that all the ionic liquids studied can be considered moderately hydrogen-bond acid and highly cohesive stationary phases, on which the dominant contributions to retention were the dipolar-type and hydrogen-bond base interactions, while π-π and n-π interactions were barely significant. The SLB-IL59 column provided the best separation of homologs, while the SLB-IL76 and SLB-IL100 columns had the most basic and the most acidic phases, respectively. A principal component analysis for the commonly used stationary phases in capillary GC showed that these commercial ionic liquid columns fill an empty area of the available selectivity space, which clearly enhances the separation capacity of this technique.