Poly(dimethylsiloxane)-poly(ethylene oxide) (PDMS-PEO) diblock copolymer has been used as template in methylphenylsiloxane (MPS) resin matrix to fabricate porous MPS/PDMS composite. The structure of resulting materials has been characterized by transmission electron microscopy (TEM), nitrogen-sorption measurements, and (1)H NMR. Experiments show that MPS/PDMS composites with pore structures and large pore sizes have been obtained. The BET surface area, pore volume, and mean pore size of porous MPS/PDMS composites are calculated to be 285 m(2)/g, 0.21 cm(3)/g, and 24.2 nm, respectively.