Surface enrichment of regularly arranged C atoms on carbon steel (C-steel) substrates is intriguing but challenging due to the strong bonding force between C and Fe and complex C solubility in C-steel. We propose a novel strategy of introducing a supersaturated C isolating layer on the surface of C-steel to block the ceaseless C dissolution in bulk metal and directly grow graphene on C-steel through a controlled cooling process with selected C sources for the first time. The as-grown graphene films have strong atomic coupling with the adjacent C-steel substrate, and the presence of a gradient, structured cementite layer indicates a C diffusion blocking effect for the bulk. Finally, the novel composite exhibited an exceptional anti-icing ability.