A simple, quick, and sensitive capillary electrophoretic technique-large volume stacking simple, using the electroosmotic flow (EOF) pump (LVSEP) - has been developed for determining ethylenediaminetetraacetic acid (EDTA) in drinking water for the first time. It is based on a precapillary complexation of EDTA with Fe(III) ions, followed by large-volume sample stacking and direct UV detection at 258 nm. The curve of peak response versus concentration was linear from 5.0 to 600.0 mug/L, and 0.7 to 30.0 mg/L. The regression coefficients were 0.9988 and 0.9990, respectively, The detection limit of the current technique for EDTA analysis was 0.2 mug/L with an additional 10-fold preconcentration procedure, based on the signal-to-noise ratio of 3. As opposed to the classical capillary zone electrophoresis (CE) method, the detection limit was improved about 1000-fold by using this LVSEP method. To the best of our knowledge, it represents the highest sensitivity for EDTA analysis via CE. Several drinking water samples were tested by this novel method with satisfactory results.