Mixed-phase diamond/β–SiC composite films with compositional gradient were prepared by microwave plasma-assisted chemical vapor deposition using a gas mixture of hydrogen, methane and tetramethylsilane (TMS). Single-crystalline silicon wafers, pretreated with diamond nanoparticles before deposition, were used as substrates. The film characterization by scanning electron microscopy, electron probe microanalysis, and energy-dispersive x-ray analysis shows that the contents of diamond and silicon carbide in the films vary with TMS flow rate. Diamond/β–SiC composite films with compositional gradients are achievable by varying the TMS flow rate during the film growth process.