The development of homochiral materials for the enantioselective detection and separation of chiral drugs is in high demand for the pharmaceutical industry. Herein, an anionic homochiral metal-organic framework (HMOF) with in situ generated [Me2NH2]+ counterions, {[Me2NH2]2[Zn2(d-L)2(HCO2)(OH)]·5H2O}n (HMOF-1), was synthesized using a d-camphorate-derived enantiopure dicarboxylate ligand, 4,4'-[[(1R,3S)-1,2,2-trimethylcyclopentane-1,3-dicarbonyl]bis(azanediyl)]dibenzoic acid (d-H2L) via a simple solvothermal method. Interestingly, HMOF-1 could be used as a parent framework to encapsulate Eu3+ cations via an ion-exchange process, yielding an Eu3+@HMOF-1 composite with dual-luminescent centers. The obtained Eu3+@HMOF-1 has high chemical stability and good luminescence stability in water. Importantly, Eu3+@HMOF-1 exhibits enhanced enantioselectivity and sensitivity in the detection of an important chiral nitroimidazole antibiotic, (R/S)-ornidazole (ONZ) in comparison to HMOF-1 under the same aqueous conditions. The enantiomeric excess (ee) value of the ONZ enantiomers can be accurately determined by the ratio of dual emission from the ligand and Eu3+. In addition, Eu3+@HMOF-1 shows the enantioselective separation of racemic ONZ enantiomers with an ee value of 86.6%. This work provides a simple strategy for the preparation of LnIII-incorporated HMOF composite materials for the simultaneous enantioselective detection and separation of chiral drugs.