Pharmaceutical iron sucrose is an iron (III) replacement for the treatment of iron deficiency anemia in patients with chronic kidney disease. The drug product (injection) is a colloidal solution of ferric hydroxide in complex with sucrose, containing 20 mg/mL elemental iron; according to United States pharmacopoeia (USP), the limit of iron (II) is 0.4% w/v. A selective CE method for the simultaneous determination of iron (III) and its potential impurity iron (II), was developed by applying a dual precapillary complexation. In particular, 1,10-phenanthroline and 1,2-diaminocyclohexanetetraacetic acid were used for complexation of iron (II) and iron (III), respectively. Sample preparation was optimized to achieve mineralization of pharmaceuticals using HCl 6 M, by avoiding perturbation of the oxidation status of both iron species. Simple CZE conditions, involving a 60 mM (pH 9.3) tetraborate buffer at the constant voltage of 25KVand 25 degrees C, allowed fast separation of iron (II) and iron (III) complexes that were detected at 265 nm. Sensitivity for iron (II) determination was found to be 4.80 mu M (LOQ) corresponding to 0.15% w/w with respect to the total iron test level. The method was validated by following International Conference on Harmonization guidelines for specificity, linearity, precision, accuracy, and robustness and it was applied to real pharmaceutical samples. The obtained results suggested that the method can be a useful alternative to the official USP and British pharmacopoeia polarographic method.