A method to manufacture composites ZrCSiCp using a polymer‐derived ceramic route for SiC is reported. The key point of this approach was the use of SiC precursor polymers synthesized from a vinylsilane monomer, to enhance organic–inorganic interactions between ZrC mineral phase and the polymer. The results were compared with a commercial polycarbosilane, the polycarbomethylsilane. After heat treatment until 1400 °C, XRD analysis indicated the formation of a β‐SiC phase in presence of ZrC. SEM observations emphasized the role of the polymer structure on the final microstructure. The mechanisms of thermal and chemical cross‐linking were investigated, as well as the thermal behaviour of polymers.