Abstract: In order to obtain the polymer porous materials with excellent performances, under the existence of end-capping reagent hexamethyldisiloxane (MM), MTQ organic silicone resin with methacryloxypropyl functional group was prepared by hydrolytic condensation polymerization reaction between sodium silicate and methacryloxypropyltrimethoxylsilane (MPS) firstly. Then, the MTQ silicone resin was used as crosslinking agent and 2-ethylhexyl acrylate (EHA) was used as monomer, MTQ silicone resin/poly 2-ethylhexyl acrylate (PEHA) polymer porous materials were prepared by high internal phase emulsions template method. Finally, the pore structure, compressive properties and thermal stability of the porous materials were investigated. The results show that the voids diameter of MTQ silicone resin/PEHA polymer porous materials prepared by using MTQ silicone resin as crosslinking agent is in the range of 4-10 μm, and the pores diameter distributes in the range of 0.3-2.0 μm. All of the voids are linked closely, the pores are uniform distributed and the channels are narrow. MTQ silicone resin content has little effects on the specific surface area and pore volume of MTQ silicone resin/PEHA polymer porous materials, but can enhance the thermal stability and compressive strength of polymer porous materials significantly, the temperature of maximum thermal decomposition rate is up to 411.5 ℃ under nitrogen atmosphere.