The industrial realization of graphene has so far been limited by challenges related to the quality, reproducibility, and high process temperatures required to manufacture graphene on suitable substrates. We demonstrate that epitaxial graphene can be grown on transition-metal-treated 6H-SiC(0001) surfaces, with an onset of graphitization starting around 450–500 °C. From the chemical reaction between SiC and thin films of Fe or Ru, sp3 carbon is liberated from the SiC crystal and converted to sp2 carbon at the surface. The quality of the graphene is demonstrated by using angle-resolved photoemission spectroscopy and low-energy electron diffraction. Furthermore, the orientation and placement of the graphene layers relative to the SiC substrate are verified by using angle-resolved absorption spectroscopy and energy-dependent photoelectron spectroscopy, respectively. With subsequent thermal treatments to higher temperatures, a steerable diffusion of the metal layers into the bulk SiC is achieved. The result is graphene supported on magnetic silicide or optionally, directly on semiconductor, at temperatures ideal for further large-scale processing into graphene-based device structures.