The ceramic coating is fabricated by laser pyrolyzing of polydimethylsiloxane precursors with titanium powder, and the compositions and structures of the products are also analyzed. The results show that, under the action of a high energy laser, there is a free radical reaction between the titanium powder and the polydimethylsiloxane, and the fabricated multiphase ceramic coating is composed of the crystalline-state SiC, TiC, TiO2 and the amorphous-state SiO2, elemental C, C6H18OSi2. The newly formed TiO2 and TiC ceramic phases can fill the pore of the ceramic coating, which makes the coating surface uniform and dense and the pore number reduced. The addition of metallic titanium powder is also conductive to reducing the mass fraction of free carbons in the multiphase ceramic coating. When the mass fraction of the titanium powder is 5.0%, the mass fractions of Si, O and C element in the coating are 74.44%, 16.48% and 6.19%, respectively.