We designed a series of 24 bowl-shaped dicyclopenta[ghi,pqr]perylene (DCPP) derivatives with an aim to establish their charge transport and optoelectronic properties in relation to some structural modifications. The descriptors such as bowl-to-bowl inversion barrier, aromaticity, frontier molecular orbitals, ionization energies, and electron affinities (EAs) were predicted and analyzed in this report. We have found that extended pi- conjugation and electron-withdrawing groups in the DCPP derivatives result in fairly high EAs (> 3.0 eV) and narrow band gaps (1.35-1.66 eV), which promote the air-stable charge injection. By modeling the crystal structures, we find that the compounds are mostly arranged in bowl-in-bowl columnar packing, which is suitable for facilitating the intermolecular charge transport in the crystal. As a result, the p-type, n-type, and even ambipolar behavior of these bowl-shaped DCPP derivatives was anticipated through the systematic screening of the operational conditions. In particular, DCPP-12 (mu h/mu e = 4.90 X 10-3/2.50 X 10(-3 )cm2 V-1 s-1) and DCPP-TES-12 (mu h/mu e = 1.04 X 10-2/1.22 X 10-2 cm2 V-1 s-1) satisfy all the criteria for ambipolar organic semiconductors. Furthermore, the high linear and nonlinear optical activities of the DCPP derivatives pave their way toward organic-based optoelectronic applications.