X-ray photoelectron spectroscopic and scanning tunneling microscopic results demonstrate that annealing of Fe/carbon-rich 6H-SiC(0001) surface between 650 and 750 °C leads to Fe intercalation under the surface carbon layer. Accompanied with the metal intercalation, the carbon nanomesh surface was transformed into a graphene surface. Moreover, the formed graphene layers always float out to the topmost surface even after deposition of more than 10 monolayer Fe, acting as a surfactant. Using graphene as the surfactant may not only promote the 2D growth but also can improve the film performance considering that graphene is stable and robust.