Abstract: Using styrene (St) as monomer and organic silicone resin with methacryloxypropyl group (MTQ) as crosslinking-agent, the MTQ/polystyrene (PS) porous composites with honeycomb, low densities and high porosity were prepared by high internal phase ratio emulsions template (HIPE) method. The effects of MTQ on microstructure, compressive properties and thermal stability of polymer porous composites were investigated. Results indicate that the MTQ/PS porous composites have three-dimensional spherical cavities and rich interconnection pores in cavities wall, connectivity is good, and the diameters of pores range from 2-9 μm with the average interconnection pores diameters of 0.35-1.85 μm. The porosity of porous materials could be controlled, and total porosity could reach as high as 92%. Additionally, the compressive strength of porous composites is 0.28-0.74 MPa, and compressive modulus is 4.86-13.54 MPa. When the MTQ to St mass ratio is 30:100, MTQ/PS porous composites with smaller cavities diameter, narrow interconnection pores, good compression properties and thermal stability could be obtained.