In this study, the effects of the packing configuration and intermolecular interaction on the transport properties are investigated based on density functional theory. Molecular design from the standpoint of a quantum-chemical view is helpful to engender favorable molecular packing motifs. The transfer integral along the orientation with pi-pi overlap is much larger than other directions without pi-pi overlap, and the mobility along this orientation is higher than that along other directions. The intermolecular interaction analyses demonstrate that hydrogen bonds play a crucial role with strong electrostatic interactions in charge transfer. There will be a synergistic relationship when the pi-pi stacking and intermolecular interaction coexist in the same direction. It turns out that intermolecular interactions are responsible for charge transport, while pi-pi stacking interactions dominate donor-acceptor transport. Incorporating the understanding of the molecular packing motifs and intermolecular interactions into the design of organic semiconductors can assist in the development of novel materials.