Abstract In amorphous organic semiconducting systems, hole and electron transfer has been considered to occur based on the overlap of highest occupied molecular orbitals (HOMOs) and that of lowest unoccupied molecular orbitals (LUMOs) between two adjacent molecules, respectively. Other molecular orbitals (MOs), HOMO−1, HOMO−2, … and LUMO+1, LUMO+2, …, have been neglected in charge transport calculations. However, these MOs could potentially contribute to charge transport. In this study, our multiscale simulations show that carriers are effectively transported not only via HOMOs or LUMOs but also via other MOs when the MOs are close in energy. Because these multiple MOs are active in charge transports, here we call them multiple frontier orbitals. Molecules with multiple frontier orbitals are found to possess high carrier mobility. The findings in this study provide guidelines to aid design of materials with excellent charge transport properties.