The structure of SCPP[8] consists of a twisted benzene ring bridged by polyphenylene units, resulting in a stable and rigid conformation. This excellent conformational stability enables complete enantiomeric resolution and characterizations. After purification by flash column chromatography, the resolution of racemic samples was achieved by a recycling HPLC system. After only two cycles, we succeeded in the isolation of the complete set of two enantiomers (P)-SCPP [8] and (M)-SCPP [8]. The extremely narrow peaks in HPLC strongly indicated excellent separation of the two enantiomers, and the molar ratio of the two isomers was determined to be approximately 1:1 (Figure ). The enantiomeric relationship of the (P)-SCPP [8] and (M)-SCPP [8] was identified using CD spectroscopy. In Figure , the CD spectrum of (M)-SCPP [8] showed two negative Cotton effects at 299 and 371 nm and two positive ones at 336 and 467 nm. Being the enantiomer of (M)-SCPP [8], (P)-SCPP [8] gave the expected mirror-imaged CD spectrum, confirming their enantiomeric relationship. The magnitude of the CD spectra can be quantified by the dissymmetry factor (gCD), which is the ratio of CD intensity to the corresponding absorption. A large |gCD| of ~0.012 was obtained for the enantiomers of SCPP [8]. To further elucidate the absolute configuration of (P)-SCPP [8] and (M)-SCPP [8], we investigated the theoretical CD spectra on the basis of TD-DFT calculations, as shown in Figure (dashed plot). The theoretical CD spectra of the resolved enantiomers were in good agreement with the experimental results. To gain insight into the configurational stability of (P)-SCPP [8] and (M)-SCPP [8], we used temperature-dependent CD spectra to investigate the conformational behavior of these two enantiomers. Chlorobenzene was chosen as the solvent as it allowed access to a wide range of temperatures. To investigate the temperature-dependence of the CD-signals, the samples were heated from -10 °C to 125 °C, and CD spectra were recorded at 15 °C intervals (Figure ). The results clearly showed that optical activity of (P)-SCPP [8] and (M)-SCPP [8] have no significant change even after heating to 125 °C. The slight change can be attributed to the influence of the solvent at different temperatures, and the change can be recovered by cooling down the solvent (Figure ). This result showed that the resolved enantiomers of SCPP [8] are configurationally stable, maintaining their optical activity in a wide range of temperatures. These rigid bismacrocycles contain nonracemizable structures, and the geometry can preclude significant loss of enantiomeric purity during further research and application processes. Therefore, the isolation and characterization of SCPP [8] enantiomers shed light on a novel scaffold of nonracemizable chiral bismacrocycles with potential applications as chiroptical material.