Several monolithic chiral stationary phases for reversed-phase electrochromatography have been prepared within the confines of untreated fused silica capillaries by the direct copolymerization of the chiral monomer 2-hydroxyethyl methacrylate (N-L-valine-3,5- dimethylanilide) carbamate with ethylene dimethacrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid and butyl or glycidyl methacrylate in the presence of a porogenic solvent. The hydrophilicity of the stationary phase, which may be enhanced further by the hydrolysis of the epoxide functionalities of the glycidyl methacrylate moieties within the monolith, was found to have a pronounced effect on the enantioseparation. Using the most hydrophilic monolithic capillary column and optimized elution conditions, a separation of N-(3,5-dinitrobenzoyl)leucine diallylamide enantiomers with an efficiency of 61000 plates m–1 and a resolution of 2.0 was achieved.