The work aims to improve ablation and toughness properties of silicone modified epoxy resin based ablation thermal protection coating. A new type of silicone modified epoxy resin was synthesized by a new synthetic method, i.e. one-step method. FT-IR was used to characterize the chemical structure of synthetic resin and study the mechanical properties and the pyrolysis temperature range of new resin matrix. On such basis, the silicone modified epoxy resin was used as the new resin matrix to prepare the ablation thermal protection coating. The mechanical properties, ablation resistance and thermal protection of coatings were also evaluated and assessed. As for toughness, the elongation at break of new silicone modified epoxy based ablation thermal protection coating increased from 1% to 8% when compared with the traditional one. For ablation property, when 1mm thick new ablation thermal protection coating was used in 304 steel at thermal flow of 200 kW/m2 and 320 s at most, the ablation surface was flat and the back temperature was only 160 ℃, while the back temperature of traditional epoxy coating was 220 ℃. The silicone modified epoxy resin can improve the ablation resistance and toughness properties of traditional epoxy based ablation and thermal protection coating.