New, solution processable organic semiconductors, namely arylene bisimides core- or N-functionalized with triarylamines have been synthesized in view of their potential application in organic electronics. In N-functionalized compounds the electrochemically determined oxidation potentials are 0.46 and 0.48 V vs Fc/Fc+ for perylene (P1) and naphthalene (N1) bisimides, respectively. For the core functionalized perylene bisimide (P2) this potential is shifted to higher values (0.55 V vs Fc/Fc+). A reversed trend is observed for the first reduction potential since P2 is being reduced at the lowest potential (−1.09 V) whereas N1 and P1 at −1.05 and −1.02 V, respectively. These shifts observed in the case of P2 are induced by donor–acceptor interactions between the substituent and the core. The results of DFT calculations performed for N-substituted bisimides indicate a clear separation in space of the HOMO and LUMO orbitals, the former being located on the triarylamine substituent whereas the latter is on the bisimide core. To a first approximation, their UV–vis–NIR spectra can be considered as a superposition of the triarylamine spectrum and those of bisimides containing nonchromophore (alkyl) substituents. This indicates a very weak or essentially nonexistent conjugation between the aromatic core and the N-substituents. In powders, the N-functionalized bisimides show liquid crystalline-type structural organization whereas in thin, spin-coated films they are amorphous. The core-substituted bisimide shows different properties. In this case a new band of a charge transfer (CT) character appears in its UV–vis spectrum. In accordance with the spectroscopic data, the DFT calculations indicate that in the core-substituted compound the HOMO electron density spreads from the triarylamine substituent to the bisimide core. Powders of the core-substituted bisimide crystallize in a 3D structure whereas thin spin-coated films show liquid crystalline-like structural organization. Taking into account their electrochemical properties, all three bisimides studied seem to be good candidates for the fabrication of air operating ambipolar transistors. However, N-functionalized bisimides show only p-type behavior with the hole mobility approaching 10–4 cm2 V–1 s–1 in the all organic (CYTOP dielectric) field effect transistor configuration. The core-substituted bisimide shows, however, the expected ambipolar behavior with the hole and electron mobilities of 1.5 × 10–3 and 3.5 × 10–4 cm2 V–1 s–1, respectively.