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A silicon-containing polymer (HMSA), synthesized with n-BuLi, trichloroethylene, dichloromethylsilane, and dimethyldichlorosilane, with three different proportions of Si–H, and its influence on thermal oxidation have been studied. The structures of HMSA were characterized by Fourier transform infrared spectra, 1H-Nuclear Magnetic Resonance (H-NMR), 13C-NMR, 29Si-NMR, and gel permeation chromatography. Thermal and oxidative stabilities were studied by differential scanning calorimetry and thermogravimetric analysis, and the cross-linking reaction mechanisms of the HMSA were discussed. All the polymers exhibited excellent thermal and oxidation resistance; particularly, HMSA-1 showed high heat-resistant and thermo-oxidative stability; the temperatures of 5% weight loss (Td5) were 636.3 and 645.5°C, and the residues at 1000°C were 87.07 and 86.23% in nitrogen and air, respectively. This system had excellent thermal and oxidative stability, and through the structure design, control of heat oxidation resistance was realized.