In this study, organic field-effect transistors (OFETs) using a naphthalene dicarboxamide (NDI)-based n-type semiconducting polymer and electrodes comprising either Au or reduced graphene oxide (rGO) were fabricated. Compared with those with Au electrodes, transistors with rGO electrodes exhibited enhanced hole transport characteristics. The analysis of the interaction between the NDI-based polymer and the two electrodes revealed satisfactory hole transport in terms of device performance with the rGO electrode despite the less favorable work function for the injection of holes into the polymer semiconductor, corresponding to the formation of interfacial dipoles of different magnitudes. The electron orbital structure of the rGO electrode induced a smaller shift by the dipole moment at the interface between the electrode and semiconductor compared with that induced by the electron orbital structure of the gold electrode to promote ambipolarity. In both cases, energy barriers for the injection of charge at the interface were determined by ultraviolet photoelectron spectroscopy and Kelvin probe force microscopy analysis. In addition, a complementary logic inverter comprising two identical OFETs based on n-type NDI derivative and rGO electrodes with improved hole transport properties was fabricated.