The electronic band structure in the epitaxial Fe/MgO/GaAs(001) tunnel junction has been studied by x-ray and ultraviolet photoelectron spectroscopy measurements. The Schottky barrier height (SBH) of Fe on MgO/GaAs heterostructure is determined to be 3.3±0.1 eV, which sets the Fe Fermi level at about 0.3 eV above the GaAs valence band maximum. This SBH is also exactly the same as that measured from Fe on MgO monocrystal. After Fe deposition, no band bending change is observed in MgO and GaAs underlayers. On the contrary, Au and Al depositions led to clear variation of the band bending in both MgO and GaAs layers. This effect is analyzed as a fingerprint of defect states at the MgO/GaAs interface.