The 3-dimensional structure of adsorption complexes on mineral surfaces provides insight into the fundamental mechanisms controlling sorption processes. This is important to the development of a general understanding of the behavior of contaminants such as selenite in the environment. The adsorption of selenite (SeO3(2-)) on the hematite (100) surface was studied using X-ray standing wave (XSW) measurements. Inner-sphere bidentate surface complexes bridging between adjacent singly-coordinated oxygen sites were identified as the primary adsorption site. The lack of binding to doubly-coordinated oxygen sites that were also exposed on the surface was likely due to differences in the reactivity or exchange kinetics of these sites or cation-cation repulsion, although the latter appears to be a secondary effect based on past observations. While these bridging bidentate geometries are similar to those inferred in past spectroscopic studies, the Se-Fe distances are such that these species might be misidentified as edge-sharing complexes if studied by EXAFS spectroscopy, highlighting the need for a fundamental understanding of mineral surface structure.