In the studies presented here, the subsequent growth of graphene on hexagonal boron nitride (h-BN) is achieved by the thermal decomposition of molecular precursors and the catalytic assistance of metal substrates. The epitaxial growth of h-BN on Pt(111) is followed by the deposition of a temporary Pt film that acts as a catalyst for the fabrication of the graphene sheet. After intercalation of the intermediate Pt film underneath the boron-nitride mesh, graphene resides on top of h-BN. Scanning tunneling microscopy and density functional calculations reveal that the moiré pattern of the van-der-Waals-coupled double layer is due to the interface of h-BN and Pt(111). While on Pt(111) the graphene honeycomb unit cells uniformly appear as depressions using a clean metal tip for imaging, on h-BN they are arranged in a honeycomb lattice where six protruding unit cells enframe a topographically dark cell. This superstructure is most clearly observed at small probe–surface distances. Spatially resolved inelastic electron tunneling spectroscopy enables the detection of a previously predicted acoustic hybrid phonon of the stacked materials. Its’ spectroscopic signature is visible in surface regions where the single graphene sheet on Pt(111) transitions into the top layer of the stacking.