The production of high-quality graphene-oxide interfaces is normally achieved by graphene growth via chemical vapour deposition on a metallic surface, followed by transfer of the C layer onto the oxide, by atomic layer and physical vapour deposition of the oxide on graphene or by ​carbon deposition on top of oxide surfaces. These methods, however, come with a series of issues: they are complex, costly and can easily result in damage to the ​carbon network, with detrimental effects on the carrier mobility. Here we show that the growth of a graphene layer on a bimetallic Ni3Al alloy and its subsequent exposure to ​oxygen at 520 K result in the formation of a 1.5 nm thick ​alumina nanosheet underneath graphene. This new, simple and low-cost strategy based on the use of alloys opens a promising route to the direct synthesis of a wide range of interfaces formed by graphene and high-κ dielectrics.