In this study, a novel hydroxypropyl‐γ‐cyclodextrin (HP‐γ‐CD) functionalized monolithic capillary column was prepared by one‐pot sequential strategy and used for chiral separation in capillary electrochromatography for the first time. In one pot, GMA‐HP‐γ‐CD as functional monomer was allowed to be formed via the ring opening reaction between HP‐γ‐CD and glycidyl methacrylate (GMA) catalyzed by 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) and then copolymerized directly with ethylene dimethacrylate (EDMA) and 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS) in the presence of porogenic solvents via thermally initiated free radical polymerization. The preparation conditions of monoliths were optimized. Enantiomer separations of six chiral drugs including pindolol, clorprenaline, tulobuterol, clenbuterol, propranolol, and tropicamide were achieved on the monolith. Among them, pindolol, clorprenaline, and tropicamide were baseline separated with resolution values of 1.62, 1.73, and 1.55, respectively. The mechanism of enantiomer separation was discussed by comparison of the HP‐γ‐CD and HP‐β‐CD functionalized monoliths.