The influence of surface-bound Fe(II) on uranium oxidation state and speciation was studied as a function of time (6 min−72 h) and pH (6.1−8.5) in a U(VI)−Fe(II)-montmorillonite (Ca-montmorillonite, MONT) system under CO2-free, anoxic (O2 <1 ppmv) conditions. The results show a rapid removal of U(VI) from the aqueous solution within 1 h under all pH conditions. U LIII-edge X-ray absorption near-edge structure spectroscopy shows that 96% of the total sorbed U(VI) is reduced at pH 8.5. However, the extent of reduction significantly decreases at lower pH values as specifically sorbed Fe(II) concentration decreases. The reduction kinetics followed by X-ray photoelectron spectroscopy during 24 h at pH 7.5 demonstrates the presence of partially reduced surface species containing U(VI) and U(IV). Thermodynamically predicted mixed valence solids like U3O8/β-U3O7/U4O9 do not precipitate as verified by transmission electron microscopy and extended X-ray absorption fine-structure spectroscopy. This is also supported by the bicarbonate extraction results. The measured redox potentials of Fe(II)/Fe(III)−MONT suspensions are controlled by the Fe(II)/hydrous ferric oxide [HFO(s)] couple at pH 6.2 and by the Fe(II)/lepidocrocite [γ-FeOOH(s)] couple at pH 7.5. The key finding of our study is the formation of a sorbed molecular form of U(IV) in abiotic reduction of U(VI) by sorbed Fe(II) at the surface of montmorillonite.