Metal-mediated exfoliation can give macroscopic (millimetre or more) monolayers of a wide range of 2D materials (2DMs). This is both a useful tool for fabrication, and an interesting opportunity for studying the intricacies of interactions at the interfaces between three-dimensional metals and 2D materials. Understanding these interactions is essential for the integration of 2DM into (opto)electronic circuits as well as for unravelling the mechanism for metal-mediated exfoliation. Here, I will present some of our recent results using template-stripped gold for metal-mediated exfoliation of 2DMs, concentrating on prototypical examples of a 2D semiconductor (WSe₂) and a 2D magnet (CrSBr). The large monolayer / few-layer flakes on ultra-flat gold that result from metal mediated exfoliation are ideally suited to study by surface science techniques. We gain insight into the Au-2DM interface through spatially resolved photoemission spectroscopy, at the I05 beamline of Diamond Light Source, both of core levels and angle-resolved of the valence bands. Contrasting results are observed for the two material systems, but both reveal the importance of charge transfer and hybridisation, consistent with covalent like quasi-bonding at the Au-2DM interface.