Vacuum cosublimation gave the first charge-transfer (CT) solid of pi-bowl corannulene as an electron donor with pi-planar 7,7,8,8-tetracyanoquinodimethane (TCNQ) as an electron acceptor, which consists of segregated and alternating columns. In the latter column, hub carbons with significant HOMO coefficients form it it interactions with adjacent TCNQ only on the convex side of the corannulene, resulting in the difference in the CT interaction between the two sides.