A novel propellane–nanoring hybrid, TPPTI-[9]CMP, was synthesized by triply combining [9]cyclo-meta-phenylene ([9]CMP) with triperyleno[3,3,3]propellane triimides (TPPTI). This structure features two [9]CMP subunits which necessarily fill the voids of TPPTI and promote assembly of the hybrid to form porous superstructure held together by attractive dispersion between the [9]CMP subunits of neighboring molecules. In the structure, three large spatial cavities are formed, which allow an efficient binding of up to three C60 within a single hybrid. The transient absorption spectroscopy revealed that TPPTI-[9]CMP and C60 interact with each other to form stable complex and produce long-lived triplet states. Notably, the hybrid can adsorb ethane (C2H6) with very excellent selectivity over ethylene (C2H4), leading to a highly selective C2H6/C2H4 separation.