© 2019 Elsevier Ltd Marine ferromanganese crusts and nodules as potential mineral deposits have received increasing attention. However, much less knowledge is available concerning the incorporation and enrichment mechanisms for antimony (Sb) and arsenic (As) in marine ferromanganese oxides. In this study, the surface complexations of Sb(V) and As(V) on synthetic ferrihydrite and Mn oxides (δ-MnO2 and birnessite) were investigated by a combination of adsorption experiments, extended X-ray absorption fine structure (EXAFS) analyses, and quantum chemical calculations. The speciation, distribution, and local structure of Sb and As in different types of natural marine ferromanganese oxides were determined by X-ray absorption near edge structure (XANES) and EXAFS analyses to reveal the enrichment mechanisms for the two elements in ferromanganese oxides at the molecular level. To the best of our knowledge, the Sb EXAFS analyses for different types of marine ferromanganese oxides are herein reported for the first time. Results showed that Sb(V) is preferentially adsorbed on Mn oxides through energetically favorable bidentate–mononuclear complexation because of the structural similarity between the octahedron SbV(OH)6− and MnO6 unit, although bidentate–binuclear (corner-sharing) and bidentate–mononuclear (edge-sharing) complexes can be formed on ferrihydrite and Mn oxides for the adsorption of Sb(V). By contrast, tetrahedral AsVO43− is mostly adsorbed on ferrihydrite and Mn oxides with the formation of bidentate–binuclear complexes. In natural marine ferromanganese oxides, Sb and As can be retained by Fe and Mn (oxyhydr)oxide components, and the disparate distribution of the two elements to Mn oxides may largely depend on the Mn/Fe ratio and constituent minerals. The larger enrichment factor of Sb than that of As in marine ferromanganese oxides may result from their preferential attachment modes onto the Fe and Mn phases and different inhibition effects from coexisting anions in seawater. Compared with As, a part of Sb may be strongly associated with the lateral sites in Mn oxides via the formation of bidentate edge-sharing complexes, with which anions such as sulfate in seawater do not significantly compete. The findings from this study provide the molecular-scale insights into the enrichment processes and mechanisms of Sb and As in marine ferromanganese oxides. Our study also helps elucidate the incorporation mechanisms and geochemical behaviors of other oxyanions in marine and surface environments.