This thesis covers in detail the literature on the theoretical aspects of electrodriven separation in capillary electrophoresis (CE) and capillary electrochromatography (CEC), the column technology of CEC including different types of stationary phases; open-tubular (coated columns), packed and continuous-bed (monolith). The literature on the coupling of CE/CEC with mass spectrometry (MS) and their advantages are also covered. The thesis also describes the preparation and the characterisation of polymethacrylate monoliths. Butyl methacrylate and sodium sulphite-based monoliths with negative surface charges were prepared: The former derived the charge from the sulfonic acid moieties of the 2-acrylamido-2-methyl-l- propanesulfonic acid (AMPS) while the second derived the charge from the sulphite group of the sodium sulphite introduced by epoxide ring opening. This negative charge is responsible for the generation of electroosmotic flow (EOF).