Organic monolithic stationary phases for CEC were synthesized in situ in fused-silica capillaries. Polymerization mixtures were composed of butyl methacrylate, ethylene dimethacrylate, and [2-(methacryloyloxy)ethyl]trimethyl ammonium chloride in the presence of a porogenic solvent, using ammonium peroxodisulfate as chemical initiator, and N,N,N',N'-tetramethylethylenediamine to activate the reaction. The influence of the amount of initiator, temperature, and composition of porogenic solvent on the physical and chromatographic properties of monolithic stationary phases has been investigated. A minimum plate height of 14.5 microm was obtained at 18 wt% of 1,4-butanediol in the polymerization mixture. The produced monolithic stationary phases exhibited a good repeatability and batch-to-batch and mixture-to-mixture reproducibility, with RSD values below 5.6% in the electrochromatographic parameters studied. A comparison with columns prepared by thermal initiation with alpha,alpha'-azobisisobutyronitrile (AIBN) was also performed. The most efficient column initiated with peroxodisulfate showed better efficiencies and selectivities than that prepared with AIBN at the same composition mixture.