The (001) surface of magnetite has been studied using Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). A clean, octahedrally terminated surface was obtained by a combination of in‐situ annealing in an O2atmosphere, Ar+ion etching and subsequent annealing in UHV. LEED exhibits a (&sqrt2; × &sqrt2;)R45° mesh. STM was carried out with probes made from antiferromagnetic MnNi. Atomically resolved images of the octahedrally terminated surface show rows, running along the [110] direction, separated by 6 Å. Along these rows two different atomic scale features are imaged, with a periodicity of 6 Å, as opposed to the 3 Å periodicity of the Fe ions expected for bulk terminated magnetite (001). A model explaining the observed symmetry in terms of charge ordering of the Fe2+and Fe3+cations, on the surface octahedral sites, is proposed. © 2003 American Institute of Physics