Artificial 2D van der Waals heterostructures with controllable vertical stacking and rotational orientation exhibit multifaceted electronic properties that are appealing for applications in fields ranging from optoelectronics to energy storage. Along with transition metal dichalcogenides and graphene, borophene has recently emerged as a promising building block for 2D devices due to its conductive nature as well as its exceptional mechanical and electronic properties. Here, it is demonstrated that the combination of the dissolution-segregation process and chemical vapor deposition allows for the synthesis of graphene/borophene heterostructures of the highest crystalline and chemical quality, in which graphene sits on top of the borophene layer with metallic character. The formation of laterally distinct micron-sized areas allows a comparative study of borophene, graphene, and the graphene–borophene heterostack in terms of their electronic properties and stability in a reactive environment. Whereas pristine borophene is particularly prone to oxidation, the graphene–borophene heterostack is chemically inert and enables the conservation of borophene's character even after exposure to air. This study opens up new perspectives for the scalable synthesis of graphene–borophene heterostacks with enhanced ability to preserve the metallic character and electronic properties of borophene.