The complexation equilibria of iron(III) with 3-hydroxypicolinic acid (hypa) have been studied spectrophotometrically in 40% (v/v) ethanol-water medium at 25 degrees C and an ionic strength of 0.1 M NaClO4. The equilibria occurring in solution were established and the basic characteristics of the complexes formed were determined. The spectral study of the reaction solutions containing equimolar concentrations or an excess of one component in the pH range 1.5 to 10.5 gave the evidence for the formation of [FeLH]2+, [FeL]+ and [FeL2]- complex species, depending upon the pH of the medium (LH2 symbolising the molecular form of hypa). The possible complex transitions that occur in solution were demonstrated using graphical and logarithmic analysis of the absorbance-pH graphs. A simple, rapid, sensitive and selective method for spectrophotometric determination of trace levels of iron(III) was proposed based on the formation of Fe(hypa)2 complex at pH 5.5 (lambda = 440 nm, epsilon = 1.5 x 10(4) dm3 mol-1 cm-1). The interference of a large number of foreign ions was investigated. The method has been applied successfully to the analysis of multivitamin and mineral preparations containing iron.