The selective formation of large-scale graphene layers on a Rh-YSZ-Si(111) multilayer substrate by a surface-induced chemical growth mechanism is investigated using low-energy electron diffraction, X-ray photoelectron spectroscopy, X-ray photoelectron diffraction, and scanning tunneling microscopy. It is shown that well-ordered graphene layers can be grown using simple and controllable procedures. In addition, temperature-dependent experiments provide insight into the details of the growth mechanisms. A comparison of different precursors shows that a mobile dicarbon species (e.g., C(2)H(2) or C(2)) acts as a common intermediate for graphene formation. These new approaches offer scalable methods for the large-scale production of high-quality graphene layers on silicon-based multilayer substrates.