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In this chapter, we review the recent results on graphene films epitaxially grown on 3d -5d transition-metal surfaces focussing mainly on their atomic structure, aspects of chemical interaction both with the substrate and with adsorbates and the electronic structure of graphene at the interface. We discuss a possibility to prepare sandwich-like structures in the form of intercalates as a possible way to controllably tailor the electronic properties of graphene. Recent works on the templateddoi:10.1007/978-3-642-22984-8_7 fatcat:7pgmfsetdvcunml4hj4sdfqqp4