The X-ray reflectivity technique can provide out-of-plane electron-density profiles of surfaces, interfaces, and thin films, with atomic resolution accuracy. While current methodologies require high surface flatness, this becomes challenging for naturally curved surfaces, particularly for liquid metals, due to the very high surface tension. Here, the development of X-ray reflectivity measurements with beam sizes of a few tens of micrometres on highly curved liquid surfaces using a synchrotron diffractometer equipped with a double crystal beam deflector is presented. The proposed and developed method, which uses a standard reflectivity θ–2θ scan, is successfully applied to study in situ the bare surface of molten copper and molten copper covered by a graphene layer grown in situ by chemical vapor deposition. It was found that the roughness of the bare liquid surface of copper at 1400 K is 1.25 ± 0.10 Å, while the graphene layer is separated from the liquid surface by a distance of 1.55 ± 0.08 Å and has a roughness of 1.26 ± 0.09 Å.