Vertical distributions of iron and iron binding ligands were determined in 2 size classes (dissolved <0.2μm, soluble <200kDa, e.g., ~0.03μm) in the Southern Ocean. Colloidal iron and complexing capacity (>200kDa–<0.2μm) were inferred as the difference between the dissolved and soluble fractions. Dissolved iron and ligands exist primarily in the soluble size range in the surface waters, although iron-complexing colloids still represent a significant portion of the dissolved pool and this fraction increases markedly with depth. This work presents evidence for the colloidal nature of a significant portion (37–51% on average) of the ‘dissolved’ organic Fe pool in these oceanic waters. From the data it was not possible to discern whether iron colloids exist as discrete organic complexes and/or inorganic amorphous colloids. Iron-complexing colloids are the most saturated with iron at the thermodynamic equilibrium, whereas soluble organic ligands occur in larger excess compared to soluble iron. It suggests that the exchangeable fraction for iron uptake through dissociation of Fe complexes likely occurs in the soluble fraction, and that soluble ligands have the potential to buffer iron inputs to surface waters whereas iron colloids may aggregate and settle. Expectations based on Fe diffusion rates, distributions and the stability of the soluble iron complexes and iron colloids also suggest that the weaker soluble Fe complexes may be more bio-available, while the strongest colloids may be a major route for iron removal from oceanic waters. Investigations of the size classes of the dissolved organic iron thus can significantly increase our understanding of the oceanic iron cycle.