Molecular electronic junctions fabricated by covalent bonding onto a graphitic carbon substrate were examined with Raman spectroscopy and characterized electronically. The molecular layer was a 4.5 nm thick multilayer of nitroazobenzene (NAB), and the top contact material was varied to investigate its effect on junction behavior. A 3.0 nm thick layer of copper, TiO₂, or Al(III) oxide (AlO_x) was deposited on top of the NAB layer, followed by a 7.0 nm thick layer of gold. Copper “contacts” yielded molecular junctions with low resistance and showed a strong dependence on molecular structure. Carbon/NAB/AlO_x/Au junctions exhibited high resistance, with current densities three orders of magnitude less than those for analogous Cu junctions. However, Raman spectroscopy revealed that the NAB layer was reduced when the carbon substrate was biased negative, to a product resembling that resulting from electrochemical reduction of NAB. Carbon/NAB/TiO₂/Au junctions showed rectifying J/V behavior, with high conductivity to electrons able to enter the TiO₂ conduction band. Substitution of azobenzene for nitroazobenzene yielded junctions with similar spectroscopic and electronic behavior to NAB, indicating that the nitro group is not essential for rectification. The results are interpreted in terms of the energy levels of the molecule relative to those of TiO₂. The combination of a covalently bonded molecular layer and a semiconducting oxide yields unusual electronic properties in a carbon/molecule/semiconductor/Au molecular junction.