The surface and interface structure as well as the electronic properties of thin epitaxial Fe 3 O 4 (111) films prepared by in situ oxidation of thin Fe͑110͒ films grown on Al 2 O 3 (112 0) substrates using a Mo͑110͒ buffer layer were investigated by low-energy electron diffraction ͑LEED͒, scanning tunneling microscopy ͑STM͒, transmission electron microscopy ͑TEM͒, and spin-polarized angle-resolved photoemission spectroscopy ͑SPARPES͒. The annealing of Fe͑110͒ films at 700°C in an O 2 atmosphere leads to the formation of epitaxial