Though it is clear that plankton in oceanic regions access iron bound to strong organic ligands, the mechanism mediating the release of iron from these complexes remains unresolved. In this study, we aim to elucidate the mechanisms of organic iron acquisition by plankton in subantarctic waters. In particular, we investigated the importance of photochemistry in mediating the reductive dissociation of iron from organic complexes, using naturally occurring ligands, and model iron complexes, with different iron-binding groups and photoreactivities. Our results demonstrate that iron within the model ligands is available for uptake and growth by indigenous plankton, but that photolability of these complexes does not determine iron bioavailability. In contrast, light significantly enhances iron acquisition from the in situ ligands, suggesting that the in situ iron ligands are photolabile, and that photochemistry in surface waters may play a significant role in iron uptake from the dissolved organic iron pool by oceanic plankton.