We investigated the resistance switching (RS) phenomenon in epitaxial NiO (epi-NiO) films by employing different types of top electrodes (TEs). Epi-NiO showed successive bipolar RS when Pt and CaRuO3 (CRO) were used as the TEs, but not when Al and Ti were used. We studied the temperature dependence of the current–voltage (I–V) characteristics for various TEs and resistance states to understand the conduction properties of TE/epi-NiO. Pristine CRO/epi-NiO showed metallic behavior, while pristine Pt/epi-NiO and Al/epi-NiO showed insulating behavior. Pt/epi-NiO and Al/epi-NiO, however, switched to a metallic or non-insulating state after electroforming. Transmission electron microscopy (TEM) images revealed the presence of a distinct stable interfacial AlO
x
layer in pristine Al/epi-NiO. On the other hand, the interfacial metal oxide layer was indistinguishable in the case of pristine Pt/epi-NiO and CRO/epi-NiO. Our experimental results suggested that epi-NiO has an oxygen defect on its surface and therefore the various TE/epi-NiO interfaces characterized in this study adopt distinctive electrical states. Further, the bipolar RS phenomenon can be explained by the voltage-polarity-dependent movement of oxygen ions near the interface.