In this study we report a new, simple and efficient method for the synthesis of a silica monolithic chromatography column. Instead of the usual base corrosion method, a template induced synthesis method was used to create bimodal pores in the column bed. Block polymer Pluronic F127 was used as a dual-function template to form a hierarchically porous silica monolith with both macropores and mesopores. The surface of the silica monolithic column bed was modified in situ by the C18 reagent, and was then evaluated by the μ-HPLC method. 30 000–40 000 theoretical plates per m were observed indicating that the new synthesis method creates a monolithic material that can act as an efficient chromatographically stationary phase. The method also makes the fabrication of silica monolithic columns (especially capillary columns) much simpler.