The mechanism of graphitic ordering of atomic C on Ni was investigated at temperatures ranging from room temperature to 550 °C. The C/Ni films were prepared by ion beam sputtering. Their structure has been determined by Rutherford backscattering spectrometry/nuclear reaction analysis, X-ray photoelectron spectroscopy, Raman spectroscopy and cross-sectional transmission electron microscopy. A temperature-induced and a Ni-induced enhancement of graphitic ordering is demonstrated. The Ni-effect is responsible for the formation of a bi-layer structure of the C films at higher deposition temperatures. In the bi-layers, C forms graphenic planes parallel to the Ni surface within a thickness range of 1–2 nm. Further deposited C grows preferentially perpendicular to the surface. The results are discussed on the basis of hyperthermal atom deposition, surface diffusion, metal-induced crystallization and dissolution-precipitation. Our findings point to a dominating role of surface diffusion-assisted crystallization in the carbon ordering process.