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Molybdenum (Mo) is a key trace element and a contaminant in many environments including mine tailings and acid mine drainage systems. Under oxic conditions Mo exists in a number of forms, including mono-molybdate (Mo(VI)O 4 2-) and various poly-molybdate species (e.g. Mo(VI) 7 O 24 6-) depending on the geochemical conditions (e.g. pH). The mobility and bioavailability of Mo is often controlled by sorption to mineral surfaces, including iron (oxyhydr)oxides e.g. hematite (Fe 2 O 3). This study uses adsorption isotherms, PHREEQC geochemical modeling, Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR), and X-ray Absorption Spectroscopy (XAS) to holistically characterise the molecular scale adsorption of molybdate to hematite as a function of pH (3−12) and Mo(VI) concentration (0.01 × 10−4 - 2 × 10−3 M). PHREEQC and ATR-FTIR indicated both pH and Mo concentration are important variables when forming mono- vs. poly- molybdate and suggest low pH (≤ 4) and high Mo(VI) concentration (≥ 5 × 10−4 M) contribute to the formation of a poly-molybdate surface species on the hematite surface. XAS found Mo adsorbed to hematite via an inner-sphere corner-sharing bidentate binuclear complex with an octahedral mono-molybdate structure at a Mo concentration of 0.6 × 10−4 M across the pH range, and at a Mo(VI) concentration of 5 × 10−4 M and pH over 5. This is the first direct observation of octahedrally coordinated Mo(VI) adsorption species on hematite, and this information has broad implications for the mobility and transport of Mo as a contaminant in the environment. [Display omitted] • Mo(VI) forms octahedral inner sphere adsorption complexes on hematite surface. • Polymolybdate is present at higher [Mo(VI)] and lower pH. • Monomeric surface complexes form at lower [Mo(VI)] and higher pH. • Implications for mobility and transport of Mo(VI) in the environment. [ABSTRACT FROM AUTHOR]