The electronic structures at the MoO(3)∕Co interface were investigated using synchrotron-based ultraviolet and x-ray photoelectron spectroscopy. It was found that interfacial chemical reactions lead to the reduction of Mo oxidation states and the formation of Co-O bonds. These interfacial chemical reactions also induce a large interface dipole, which significantly increases the work function of the cobalt substrate. In addition, two interface states located at 1.0 and 2.0 eV below the Fermi level are identified. These two states overlap at film thickness of between 2-4 nm, which suggests the MoO(3) intermediate layer may facilitate ohmic charge transport.