In this work, a novel capillary column (C4A‐mPEG) with a calixarene‐based polymer stationary phase (poly(ethylene glycol) methyl ether‐functionalized 4‐tert‐butylcalix[4]arene) was designed and used for gas chromatographic (GC) separations. The C4A‐mPEG capillary column, prepared by the static coating method, showed moderate polarity and a column efficiency of 2332 plates/m, determined by 1‐octanol at 120 °C. The separation features of C4A‐mPEG stationary phase, resulting from its unique structure and multiple molecular recognition processes with analytes, including π‐π, H‐bonding, dipole‐dipole, and van der Waals interactions, allowed to obtain high‐resolution performances for a wide range of compounds and their isomers, especially benzaldehydes, phenols, and anilines. Moreover, compared with 4‐tertbutyl calix[4]arene (C4A) and polyethylene glycol (PEG) stationary phases, a higher resolving capability was also observed for the separation of toluidine and xylidine isomers.