Recently, we have described the synthesis of chiral metal-organic frameworks iPr-ChirUMCM-1 and Bn-ChirUMCM-1 and their use in enantioselective separation. Here, we demonstrate for the first time the use of a chiral solvating agent (1-phenyl-2,2,2-trifluoroethanol, TFPE) for chiral recognition in iPr-ChirUMCM-1 and Bn-ChirUMCM-1 by means of solid-state(13)C NMR spectroscopy.