The mobility and toxicity of chromium (Cr) in soil and water systems are largely controlled by its oxidation state and interactions with solid phases. Relative to abiotic minerals, biogenic iron (Fe) (oxyhydr)oxides (BIOS) may enhance Cr(vi) adsorption and reduction due to their poorly ordered structures, large surface areas, and incorporation of cell derived organic matter. To determine the extent and mechanisms of the reaction between Cr(vi) and BIOS, sorption isotherm and kinetic studies were conducted using two-line ferrihydrite, BIOS, and BIOS amended with 0.135 M ferrozine (an Fe(ii) chelator). X-ray absorption near edge structure (XANES) spectroscopy of BIOS reacted with Cr(vi) showed approximately 50% reduction of the total sorbed Cr from Cr(vi) to Cr(iii) after 14 days of exposure. Sorbed Cr(iii) was best fit with an organic carboxylate complex after 1 d of reaction, but after 7 d mineral-associated Cr(iii) was the predominant form. In the presence of ferrozine, Cr(vi) reduction by BIOS was inhibited, confirming a key role for Fe(ii) as the Cr(vi) reductant. However, the lack of a 3 : 1 reaction stoichiometry between Fe(ii) and Cr(iii) produced suggests roles for reaction with organic matter and Cr(v) autoreduction in Cr(iii) production. This study thus elucidates an unrecognized mechanism of Cr sequestration by ubiquitous natural Fe (oxyhydr)oxide deposits. Furthermore, the redox transformation of mobile Cr(vi) to less soluble Cr(iii) species observed in our study implies that biogenic Fe (oxyhydr)oxides in soils and natural waters may naturally attenuate Cr(vi) concentrations through sorption and reduction processes, thus limiting its transport to downstream environments.