We studied the interaction of molten Si and graphite surface during annealing in different atmospheres (CO, vacuum, Ar). The studies have shown that during annealing in CO atmosphere a composite material of SiC and graphite in a thick subsurface layer of the graphite is being formed, whereas at vacuum and Ar atmosphere the modified layer is either thin or absent. The composition and structure of both the composite material itself and the interface between the composite material and the graphite matrix were investigated using the methods of scanning electron microscopy and Raman spectroscopy. Studies have shown that the composite material obtained by this method has a branched fibrous structure consisting of small tubular layers of silicon carbide interspersed with large monocrystalline grains of silicon carbide of the cubic polytype, which leads to significant strengthening of the material. Thus the proposed method can be used to form a thermal protective, chemically resistant coating on graphite surface.