A highly sensitive photometric flow-injection method is described for the determination of iron(II, III) based on the catalytic action on the oxidative coupling of N-phenyl-p-phenylenediamine with m-phenylenediamine in the presence of hydrogen peroxide. The sensitivity of the method was enhanced by the addition of Tween 80 as a surfactant. The dynamic range was 0.5-30 ng/ml of iron(II, III) with the relative standard deviations below 3% at a sampling rate of 30 h - 1 . The proposed method was subject to few interferences from coexisting metal ions and was successfully applied to the determination of iron in natural water samples.