During the Kerguelen Ocean and Plateau compared Study (KEOPS; January–February 2005) cruise, the area southeast of the Kerguelen Archipelago in the Indian sector of the Southern Ocean was investigated to identify the mechanisms of natural iron fertilization of the Kerguelen Plateau. In this study, the organic speciation of Fe is described. Samples were determined immediately on board using competing ligand-adsorptive cathodic stripping voltammetry (CL-AdCSV). The dissolved organic ligands were always in excess of the dissolved Fe concentration, increasing the residence time in the water column and the potential availability for phytoplankton. The concentration of the dissolved organic ligands ranged from 0.44 to 1.61 nEq of M Fe (=complexation site for Fe), with an average concentration of 0.91 nEq of M Fe (S.D.=0.28, n=113) and a mean logarithm of conditional stability constant (log K′) of 21.7 (S.D.=0.28, n=113). A second weaker dissolved organic ligand group was detected in 32% of the samples, with Fe-binding characteristics at the edge of the detection window of the applied method. The occurrence of the highest concentrations of dissolved organic ligands in the wind-mixed surface layer and near the sediment at the bottom of the water column indicated that both phytoplankton and the sediment act as sources. Both sources are in concert with the general conclusions from the KEOPS research on the sources of Fe, where Fe was regenerated, organic Fe-binding ligands were formed in the upper layers, and both Fe and ligands were supplied by the sediment.