Reduced terminations of the Fe3O4(001) surface were studied using scanning tunneling microscopy, x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). Fe atoms, deposited onto the thermodynamically stable, distorted B-layer termination at room temperature (RT), occupy one of two available tetrahedrally coordinated sites per (√2×√2)R45 unit cell. Further RT deposition results in Fe clusters. With mild annealing, a second Fe adatom per unit cell is accommodated, though not in the second tetrahedral site. Rather both Fe atoms reside in octahedral coordinated sites, leading to a \"Fe-dimer\" termination. At four additional Fe atoms per unit cell, all surface octahedral sites are occupied, resulting in a FeO(001)-like phase. The observed configurations are consistent with the calculated surface phase diagram. Both XPS and DFT+U results indicate a progressive reduction of surface iron from Fe3+ to Fe2+ upon Fe deposition. The antiferromagnetic FeO layer on top of ferromagnetic Fe3O4(001) suggests possible exchange bias in this system. Published by the American Physical Society under the terms of the http://creativecommons.org/licenses/by/3.0/ Creative Commons Attribution 3.0 License. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.