It has recently been shown that well-ordered Fe 3 O 4 (111) films can be prepared epitaxially on clean Pt͑111͒ surfaces; various techniques have indicated that these multilayer films are chemically identical to bulk single crystals. We have studied the electronic structure of such an ordered Fe 3 O 4 (111) film using angle-resolved photoemission in conjunction with synchrotron radiation. The valence-band structure along the ⌫L symmetry line and the resonant emission enhancement across the Fe 3 p→3d excitation threshold have been examined in detail both above ͑at 300 K͒ and below ͑at 90 K͒ the Verwey transition temperature (ϳ120K) for magnetite. The observed band dispersion agrees reasonably well with band-structure calculations for the high-temperature phase, particularly near the Fermi level, suggesting that Fe 3 O 4 should be treated with band theory. Subtle differences in the valence-band structure are observed between the two temperatures, which may be attributed to a structural change and/or a charge ordering associated with the Verwey transition. The resonant behavior shows, however, no temperature dependence, indicating that resonant photoemission in Fe 3 O 4 remains a localized process and is not influenced by the Verwey transition. ͓S0163-1829͑98͒01231-4͔