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Metal-organic frameworks (MOFs) have received great attention because of their unusual properties and fascinating structures in separation sciences. However, to the best of our knowledge, there has been no attempt to utilize chiral MOFs as stationary phases in packed-CEC. Here, a chiral MOF [In3 O(obb)3 (HCO2 )(H2 O)]·solvent (4,4'-oxybisbenzoic acid) was explored as the chiral stationary phase in packed-CEC for separation of chiral compounds and isomers. The fabricated [In3 O(obb)3 (HCO2 )(H2 O)]·solvent packed capillary columns gave fast enantioseparation of (±)-hydrobenzoin, (±)-1-phenyl-1,2-ethanediol, and clenbuterol within 3 min in CEC. Besides, the baseline separations of nitrophenol isomers within 6 min were also achieved. The RSDs for the retention time of run-to-run, day-to-day, and column-to-column reproducibility were 1.51-3.63, 1.83-3.98, and 3.42-5.66%, respectively. These results demonstrate that chiral MOFs are promising for enantioseparation in CEC.