Chiral metal‐organic frameworks have shown great potential in enantioselective separation and asymmetric catalysis due to their diverse and adjustable structures with abundant chiral recognition sites. Herein, a new chiral post‐synthetic modification was used for preparing an achiral@chiral metal‐organic frameworks core‐shell composite [Cu3(Btc)2]@[Cu2((+)‐Cam)2Dabco] by a superficial chiral etching method. The [Cu3(Btc)2]@[Cu2((+)‐Cam)2Dabco] composite was utilized as a novel chiral stationary phase for HPLC enantioseparation. Various racemates were separated on the [Cu3(Btc)2]@[Cu2((+)‐Cam)2Dabco]‐packed column (column A). It exhibited good chiral resolving ability toward many different kinds of racemates, especially chiral drugs. Among them, the highest resolution value for 1,2‐diphenyl‐1,2‐ethanediol reaches 2.70. The relative standard deviations of retention time and peak area for repeated separation of 1,2‐diphenyl‐1,2‐ethanol were 0.45% and 0.81%, respectively. Compared with the resolution ability of [Cu2((+)‐Cam)2Dabco]‐packed column (column B), column A shows higher column efficiency and better separation performance than those of column B. The results indicated that the [Cu3(Btc)2]@[Cu2((+)‐Cam)2Dabco] as a stationary phase can greatly improve the column efficiency and chiral resolution ability of chiral metal‐organic frameworks, which demonstrated that the superficial chiral etching as an economic and efficient strategy opens up a new way for the application of metal‐organic frameworks.