In this work, Fe(VI) (or ferrate) was generated by electrochemical oxidation of iron electrodes, made by pressing iron (99.5%) powder, in 14 M NaOH at room temperature. For comparison purpose, an iron foil electrode was also used to evaluate the effect of porosity on the yield for Fe(VI) generation. The cyclic voltammograms (CVs) of pure iron pellet revealed a broad anodic wave between −1 and 0.5 V versus Hg/HgO corresponding to iron dissolution and passivation of the electrode. These processes are followed by an irreversible oxidation wave attributed to the oxygen evolution reaction (OER) and the generation of ferrate. On the return scan, the cathodic wave at about 0 V versus Hg/HgO is associated with the reduction of electrochemically generated ferrate. The electrochemical generation of ferrate occurred with higher concentration and yield at an iron pellet electrode than at a foil electrode due to the porous structure of the pellet electrode, which favors iron dissolution. However, the electrochemically active thickness of the pellet electrode was estimated to be only about 1% of the actual pellet thickness.