Despite the great advances in the synthesis of diverse nonplanar graphenoids, investigations into the relationship between structural features and intermolecular interactions still present significant challenges. Herein, the novel nonplanar graphenoid structure, corannurylene pentapetalae (CRP), obtained via bottom-up syntheses of hybridization between perylene diimide (PDI) planar fragments and a corannulene curved core, is presented. Single crystal studies reveal a D-5-symmetric as well as a C-2-symmetric graphenoid corannurylene pentapetalae. The D-5-symmetric structure has a unique honeycomb lattice with two chiral honeycomb layers alternately stacked, whereas the C-2-symmetric CRP forms dimer units via pi-pi stacking. Transistor devices demonstrate that, without any pi-pi stacking, the honeycomb lattice of the D s symmetric CRP has the potential to also facilitate electron transport.