In this study, Al2O3–Cu/35Mo composites were prepared by rapid hot-press sintering-internal oxidation method, and the materials were modified by adding trace amounts of graphene oxide (GO). The results show that the relative densities of the composites are above 99%, the γ-Al2O3 generated by internal oxidation is diffusely distributed on the copper matrix. The incorporation of GO produced a small number of hard MoC particles at the interface, which facilitated the interfacial bonding of the composites. In the 30 V DC, 10–30 A electrical contact test, the anode mass of the composites increases, while the cathode mass decreases. And GO reduces the total mass loss of the electric contact by 63.6%, 38.9%, 51.3% and 20.9%, respectively. A comparison of the electrical contact properties of the two materials showed that the addition of GO dispersed the concentrated erosion of the arc. At 10 A and 30 A, the arc energy is reduced by 75.5% and 12.5%, respectively. With the gradual increase in electric current, GO makes the Al2O3–Cu/35Mo composites more stable during the electric contact process, improves the anti-welding ability of the contact and reduces contact resistance.