In this paper, a silica monolith was prepared as the promising candidate for HPLC separations. Characterization of prepared silica monolith was performed with scanning electron microscopy and surface area machine. Its chromatographic properties were evaluated by using toluene and phenol as samples while nhexane as the mobile phase. Permeability and column pressure drop were evaluated for separation, and the possible separation mechanism was also investigated in the paper. The results showed that the silica monolith had characters of high permeability, high mechanical strength, good chemical stability and strong absorption capability.