Resistive switching characteristics by using the Al2O3 interfacial layer in an Al/Cu/GdOx/Al2O3/TiN memristor have been enhanced as compared to the Al/Cu/GdOx/TiN structure owing to the insertion of Al2O3 layer for the first time. Polycrystalline grain, chemical composition, and surface roughness of defective GdOx film have been investigated by transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and atomic force microscopy (AFM). For bipolar resistive switching (BRS) characteristics, the conduction mechanism of high resistance state (HRS) is a space-charge limited current for the Al/Cu/GdOx/TiN device while the Al/Cu/GdOx/Al2O3/TiN device shows Schottky emission. However, both devices show Ohmic at a low resistance state (LRS). After the device has been SET, the Cu filament evidences by both TEM and elemental mapping. Oxygen-rich at the Cu/GdOx interface and Al2O3 layer are confirmed by energy dispersive X-ray spectroscopy (EDS) line profile. The Al/Cu/GdOx/Al2O3/TiN memristor has lower RESET current, higher speed operation of 100 ns, long read pulse endurance of >109 cycles, good data retention, and the memristor with a large resistance ratio of >105 is operated at a low current of 1.5 µA. The complementary resistive switching (CRS) characteristics of the Al/Cu/GdOx/Al2O3/TiN memristor show also a low current operation as compared to the Al/Cu/GdOx/TiN device (300 µA vs. 3.1 mA). The transport mechanism is the Cu ion migration and it shows Ohmic at low field and hopping at high field regions. A larger hopping distance of 1.82 nm at the Cu/GdOx interface is obtained as compared to a hopping distance of 1.14 nm in the Al2O3 layer owing to a larger Cu filament length at the Cu/GdOx interface than the Al2O3 layer. Similarly, the CRS mechanism is explained by using the schematic model. The CRS characteristics show a stable state with long endurance of >1000 cycles at a pulse width of 1 µs owing to the insertion of Al2O3 interfacial layer in the Al/Cu/GdOx/Al2O3/TiN structure.