Systematic studies of the gradual fabrication by means of carbon ion-implantation of high-quality 6H-SiC layers on silicon surfaces have been carried out. The fluence of carbon ions varied from 5 × 1015 cm−2 to 1017 cm−2. Results of first-principle calculations, X-ray diffraction (XRD), and Raman spectroscopy demonstrate the amorphization of silicon substrate without any tendency to the segregation of carbon in the samples synthesized at low fluencies. The formation of a SiO2-like structure at this stage was also detected. X-ray photoelectron spectroscopy (XPS), XRD, and Raman spectroscopy demonstrate that an increase in carbon content at 1017 cm−2 fluence leads to the growth of 6H-SiC films on the surface of the amorphous silicon substrate. Atomic force microscopy (AFM) data obtained also demonstrates the decreasing of surface roughens after the formation of SiC film. XPS and Raman spectra suggest that excessive carbon content leaves the SiC matrix via the formation of an insignificant amount of partially oxidized carbon nanostructures. Optical measurements also support the claim of high-quality 6H-SiC film formation in the samples synthesized at 1017 cm−2 fluence and demonstrate the absence of any detectable contribution of nanostructures formed from excessive carbon on the optical properties of the material under study.