A silica monolith column was prepared with polyethylene glycol (PEG) as a porogen, tetramethoxysilane (TMOS) as a silica precursor, as well as acetic acid and thermally decomposed urea as catalysts. The silica monolith column was then ground by a ball-mill, calcined and selected by floatation to obtain 4～6 μm silica particles. For the preparation of monolithic silica, the process was: first, 48 h reaction at 40 ℃ reaction temperature, and then another 48 h reaction at 120 ℃ reaction temperature. For the preparation of silica particles, the grinding speed was 150 r/min, and the grinding time was 1 h. The silica particles with the pore size of about 16 nm and the particle size ranged in 4～6 μm were obtained. With different modification methods on the surface of the as-prepared silica particles, a series of new stationary phases were prepared, including the surface bonded vinyl group containing C8 reverse phase, thiol-ene click reaction and free radical polymerization produced new reverse phases, and thiol-epoxy reaction generated restricted access media stationary phase. The chromatographic separation for plasticizers and drugs in bovine serum albumin (BSA) was conducted, and the results show that the packing materials so prepared have potentials for practical applications in high performance liquid chromatography (HPLC).