A C-3-symmetric chiral concave molecule having a phosphorus atom at the center was synthesized, and its enantiomers were resolved. The chiral concave shape and absolute structure of the concave molecules were revealed by X-ray analysis. The concave molecule exhibited intense chiroptical properties with a large anisotropy, which was derived from molecular orbitals delocalized to the side chains. In the co-crystal with pristine C-60, four of the enantiopure concave molecules perfectly wrapped the surface of C-60. MALDI-TOF mass, NMR, and circular dichromism spectra also supported the concave/convex interaction between the concave molecule and fullerene. These results suggest that the phosphorus-containing molecule with a concave shape plays an important role as a chiral host molecule for C-60.