Control of thin film morphology by self-assembly of, respectively, p-type oligo(p-phenylenevinylene)s (OPV)s and n-type perylenebisimides (PBI)s in solution prior to processing, results in film architectures consisting of uniform rodlike domains as shown by atomic force microscopy. Such films from self-assembled molecules show superior charge-carrier mobility in comparison with films processed from molecular dissolved molecules. Moreover, connecting the OPV and PBI building blocks through hydrogen-bonding interactions creates dyad complexes that cofacially stack in apolar solvents. Ambipolar field-effect transistors constructed from these dyad complexes show two independent pathways for charge transport. In strong contrast, processing of OPV and PBI, that are not connected by hydrogen bonds, form charge transfer donor-acceptor complexes that show no mobility in field-effect transistors presumably due to an unfavorable supramolecular organization.