Graphene substrates provide researchers with a unique and robust platform for the synthesis of new materials (i.e. 2D-metals) and heterostructures by allowing the growth of films both above and below the graphene surface, often with novel structures and properties. Depending on the elements and stacking used, these hybrid-graphene structures have applications in semiconductor electronics, superconductivity, quantum well systems, non-linear optics, and biosensing.