Chromium promotion of iron oxide based water-gas shift (WGS) catalysts prepared via co-precipitation/calcination was investigated. Mössbauer spectroscopy and XRD evidence that chromium is incorporated in the calcined hematite (α-Fe₂O₃) precursor irrespective of the doping level (0−12 wt.%). CO-TPR shows chromium delays the reduction of hematite and the active magnetite (Fe₃O₄) phase. WGS activity was evaluated under realistic conditions for 4 days. Enhanced CO conversion was observed with increased chromium doping. Mössbauer spectra indicate that chromium incorporates into octahedral sites of magnetite and prevents reduction of Fe³⁺ to Fe²⁺ during formation of the active phase, leading to an increased Fe³⁺/Fe²⁺ ratio in octahedral sites. The higher Fe³⁺/Fe²⁺ ratio did not affect the high CO conversion associated with the structural stabilization mechanism of Cr-doping. Interpretation of the Mössbauer spectra was supported by computational modelling of various chromium and vacancy-doped magnetite structures. The bulk structure of an in situ prepared chromium-doped high-temperature WGS catalyst is best described as a partially oxidized chromium-doped magnetite phase. No surface effects of Cr-doping were found.