A theoretical study using density functional theory is undertaken to gain insight into how the structural, electronic, and electron-transfer characteristics of three Fluoroarene-oligothiophene semiconductors influence the preferred transport of electrons versus holes in field-effect transistor applications. The intermolecular electronic coupling interactions are analyzed through both a simplified energy-splitting in dimer (ESID) model and as a function of the entire dimer Hamiltonian in order to understand the impact of site energy differences; our results indicate that these differences are generally negligible for the series and, hence, use of the ESID model is valid. In addition, we also investigate the reduction and oxidation processes to understand the magnitudes of the intramolecular reorganization energy for the charge-hopping process and expected barrier heights for electron and hole injection into these materials. From the electronic coupling and intramolecular reorganization energies, estimates of the nearest-neighbor electron-transfer hopping rate constant for electrons are obtained. The ionization energetics suggest favored electron injection for the system with perfluoroarene groups at the end of the thiophene core, in agreement with experiments. The combined analyses of the electron-transfer properties and ionization processes suggest possible ambipolar behavior for these materials under favorable device conditions.