A pair of homochiral zeolitic imidazolate frameworks (S(R)-ZIF-78h) materials of GME topology possessing enantiopure benzimidazolate (S(R)-OH-bim) linkers have been synthesized via solvent-assisted linker exchange (SALE) of ZIF-78, which has been confirmed through 1H NMR, element analysis, powder X-ray diffraction, gas adsorption and circular dichroism (CD). Remarkably, the S(R)-ZIF-78h materials exhibit permanent porosity and enantioselective sensing and separation towards proline.