A facile pathway has been developed to prepare silica-based micro/mesoporous bimodal hybrids with super hydrophobicity. It is the special feature of this pathway that though there are no surfactants introduced during the hydrolysis and polycondensation process, the obtained materials exhibit high specific surface areas, high porosity and bimodal structure. Actually, polymethylhydrosiloxane (PMHS), one of the silica sources, assembles itself into a special conformation and plays the role of a structure-directing agent that leads to the formation of the micro/mesophases. Thus, it is thought this novel protocol might be a profitable complement to those methods previously reported for the preparation of porous materials.