The potential of capillary zone electrophoresis (CZE) for the determination of dibutyl phosphate (DBP) and monobutyl phosphate (MBP), two degradation products of the tributyl phosphate extractant used in the nuclear fuel reprocessing industry, was evaluated. Analysis conditions were optimised, taking particularly into account that many determinations had to be performed in concentrated aqueous nitrate or nitric acid solutions. Separations were therefore carried out using the counter-electroosmotic mode with cathodic detection in a pH 8.3 electrolyte containing a suitably selected chromophore, salicylate, to ensure the indirect UV detection of the analytes. Various aspects of the method, including its sensitivity, working range, repeatability, and rapidity, were examined. Quantification of both phosphate esters was achieved in less than 3 min at concentrations ranging from 2 x 10(-6) to 10(-3) mol l(-1) in samples containing no macro-component. The lower end of this range increased to 5 x 10(-6) mol l(-1) for MBP and 1.5 x 10(-5) mol l(-1) for DBP in samples containing 5 x 10(-2) mol l(-1) of sodium nitrate, thus enabling their determination in solutions containing nitrate or nitric acid at concentrations up to, respectively, 10,000 and 3000 times higher than the target analyte concentration. This simple, fast and reliable method is routinely applicable to aqueous samples with no other preliminary treatment than a proper dilution; analysis was also performed in organic matrices after a prior extraction. The method was validated by an excellent correlation with the standard DBP analysis technique, gas chromatography (GC). In order to develop appropriate chemical treatments to destroy these compounds, the method was applied to the monitoring of DBP and MBP degradation by hydrogen peroxide in 1 mol l(-1) nitric acid solutions.