Direct iron production at molten metal state from iron oxides by the sole application of electrical energy represents a possible route to decarbonize steel industry. Although chemically simple, this reaction is difficult to implement due to the problem of the multiple valence states of iron and to an operating temperature above 1811 K. Thermal, chemical, and electrical conditions have been identified based on thermodynamic considerations to carry out this reaction in a laboratory device. Experiments were undertaken to determine the contribution of the thermal level to the decomposition of iron oxide and to estimate the electronic current resulting from iron multiple valence states. The production of liquid iron was obtained resulting in recoverable samples produced at liquid state and from a faradaic process checked in real time by its accompanying anodic oxygen evolution.