We demonstrate that freeing a single-atom thick layer of hexagonal boron nitride (h -BN) from tight chemical bonding to a Ni(111) thin film grown on a W(110) substrate can be achieved by intercalation of Au atoms into the interface. This process has been systematically investigated using angle-resolved photoemission spectroscopy, x-ray photoemission, and absorption techniques. It has been demonstrated that the transition of the h -BN layer from the "rigid" into the "quasifreestanding" state is accompanied by a change in its lattice constant. Using chemical vapor deposition, graphene has been successfully synthesized on the insulating, quasifreestanding h -BN monolayer. We anticipate that the in situ synthesized weakly interacting graphene/ h -BN double layered system could be further developed for technological applications and may provide perspectives for further inquiry into the unusual electronic properties of graphene.