Calix[4]pyrroles offer a great potential as stationary phases for gas chromatography (GC) due to their unique structures and physicochemical properties. Herein we present the first report of using two calix[4]pyrroles, namely meso-tetra-cyclohexylcalix[4]pyrrole (THCP) and meso-octamethylcalix[4]pyrrole (OMCP). These stationary phases were statically coated onto capillary columns and investigated in terms of column efficiency, polarity, separation performance, thermal stability and repeatability. The columns achieved column efficiencies of 2200–3000 plates/m and exhibited nonpolar nature with an average polarity of 67 for THCP and 64 for OMCP, respectively. THCP stationary phase shows high selectivity for analytes of different polarity and exhibits nice peak shapes, especially for aldehydes, alcohols and anilines that are prone to severe peak tailing in GC analysis. Interestingly, THCP stationary phase possesses superior resolving ability for aniline and benzenediol positional isomers while OMCP shows preferential selectivity for nonpolar analytes such as hexane isomers. Moreover, calix[4]pyrrole columns also have good thermal stability up to 260 °C and repeatability with a relative standard deviation (RSD%) of less than 0.10% for run-to-run and less than 5.2% for column-to-column. This work demonstrates the unique separation performance of calix[4]pyrroles and their promising future as a new class of GC stationary phases.