A new approach of preparingmonolithic silica column was founded by adopting an improved solgel technology with tetramethoxy silane and polyethylene glycol as the matrix materials. The reason of resulting in crack and deformation of monolith ic column was explained. By using N, N-dimethylformam ide and a heat treatment procedure, the problems of crack and deformation in preparing the column were solved and the drying time was shortened greatly. In addition, the methods of fabricating mesopore and the effects of porogen solvent of different concentrations on monolith ic silica column were investigated. The results show that the column prepared possessed bimodal pores structuresw ith micrometer-size co-continu-ous through-pores and silica skeletons which have nanometer-size mesopores, straight appearance, high porosity, good chemical and mechanical stability. The characteristics would favour the separation with a rapid speed and high efficiency for both smallmolecules and macromolecules.