The spin and orbital magnetic moments of the Fe3O4 epitaxial ultrathin film synthesized by plasma assisted simultaneous oxidization on MgO(100) have been studied with X-ray magnetic circular dichroism. The ultrathin film retains a rather large total magnetic moment, i.e., (2.73 ± 0.15) μ B/f.u., which is ∼70% of that for the bulk-like Fe3O4. A significant unquenched orbital moment up to 0.54 ± 0.05 μ B/f.u. was observed, which could come from the symmetry breaking at the Fe3O4/MgO interface. Such sizable orbital moment will add capacities to the Fe3O4-based spintronics devices in the magnetization reversal by the electric field.