The effect of chromatographic conditions on the performance of monolithic poly(butyl methacrylate-co-ethylene dimethacrylate-co-2-acrylamido-2-methyl-1-propanesulfonic acid) columns in capillary electrochromatography has been studied. The flow velocity was found to be proportional to the strength of the electric field and both the pH and the composition of the mobile phase. A column efficiency of 120,000 plates/m at the optimum flow velocity of 1.5 cm/min is achieved for all the monolithic capillary columns of identical composition and porosity, regardless of their length, which varied from 30 to 120 cm. The polymeric separation medium exhibits retention and selectivity properties similar to those of typical ODS packings for reversed-phase chromatography. In addition to the "classical" use of monolithic capillary columns for the electrochromatographic separation of small molecules in reversed-phase mode, larger styrene oligomers were also separated under isocratic elution conditions. In addition, the electroosmotically driven size exclusion chromatography of polystyrene standards with molecular weights up to 10(6) has been demonstrated for the first time.