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 D5-symmetric as well as a C2-symmetric graphenoid corannurylene pentapetalae. The D5-symmetric structure has a unique honeycomb lattice with two chiral honeycomb layers alternately stacked, whereas the C2-symmetric CRP forms dimer units via π-π stacking. Transistor devices demonstrate that, without any π-π stacking, the honeycomb lattice of the D5-symmetric CRP has the potential to also facilitate electron transport.