[en] Highlights: • The FMO energy levels of TIPSE-4P-2p is beneficial to electron and hole injection. • The electron and hole reorganization energies of are small and similar. • The crystal structure of TIPSE-4P-2p is built from the idea of homology modeling. • TIPSE-4P-2p displays ambipolar transport property in hopping and band models. The charge transport properties of phosphapentacene (P-PEN) derivatives were systematically explored by theoretical calculation. The dehydrogenated P-PENs have reasonable frontier molecular orbital energy levels to facilitate both electron and hole injection. The reduced reorganization energies of dehydrogenated P-PENs could be intimately connected to the bonding nature of phosphorus atoms. From the idea of homology modeling, the crystal structure of TIPSE-4P-2p is constructed and fully optimized. Fascinatingly, TIPSE-4P-2p shows the intrinsic property of ambipolar transport in both hopping and band models. Thus, introducing dehydrogenated phosphorus atoms into pentacene core could be an efficient strategy for designing ambipolar material.