For the first time, the possibility of creating a multilayer system metal (Al, Cr, In, Mo, and W) silicon–carbon coating was studied. A silicon–carbon film was synthesized from a polyorganosiloxane polymer containing an active Si–O siloxane group. Due to the use of furnace pyrolysis, in which the purge gas continuously removes the polymer thermal degradation products from the system, it was possible to reduce the film formation temperature to 300 °C. According to the energy dispersive analysis data, silicon–carbon film has the following composition: C—34.85 wt%, O—42.02 wt%, and Si—23.13 wt%. Metallic coatings of Al, Cr, In, Mo, and W on a silicon–carbon substrate were obtained by vacuum magnetron sputtering. The metallic coatings were evaluated by SEM as well as by X-ray phase analysis. The adhesion strength of metallic coatings to the silicon–carbon substrate was assessed by scratching under continuously increasing load with a Rockwell C Diamond Indenter. At the same time, the friction coefficient was recorded at the corresponding value of load on the indenter. The adhesive strength of metals with the silicon–carbon substrate increases in the sequence W, Mo, In, Al, and Cr.