An electrochemical cell has been used for performing in situ X-ray diffraction and absorption spectroscopy structural characterisation by transmission during electrochemical measurements. This cell has been used to reduce lepidocrocite and ferrihydrite, two iron oxides involved in low-carbon steel atmospheric corrosion mechanisms. The reduced phases have been identified in situ as magnetite and iron II hydroxide, two phases that can play a key role in corrosion mechanisms. The reoxidation of the reduced phases was also studied, and lead to the formation of magnetite/maghemite and to the formation of the initial reducible phases lepidocrocite and ferrihydrite.