Further progress in separation techniques such as HPLC and capillary electrochromatography depend largely on the development of new column technologies.Monolithic columns are successful because of their simple preparation via easily adjustable polymerization process and simple control of their chemistry.Our introduction of a photoinitiated two-step process for both preparation of the monoliths and subsequent modulation of its pore surface chemistry extended the potential of both nano-HPLC and CEC.Recently we used this technique for the preparation of open-tubular columns having inner-wall coated with a thin layer of porous poly(butyl methacrylate-co-ethylene dimethacrylate) monolithic material.The thickness of the porous polymer layer is controlled by the percentage of monomers in the polymerization mixture and/or length of the irradiation time.The layer thickness significantly affects retention, efficiency, and resolution.UV-initiated grafting of this monolith with monomers such as 2-acrylamido-2-methyl-l-propanesulfonic acid and (methacryloyloxypropyl) trimethylammonium chloride provides the column with ionizable functionalities affording the electroosmotic flow.Under optimized conditions, column efficiencies of up to 400,000 plates/m were achieved.Use of higher temperature enabled a significant acceleration of the separations.