Valence- and conduction-band edges of ultrathin oxides ( SiO2 , HfO2 , Hf0.7Si0.3O2 , ZrO2 , and Al2O3 ) grown on a silicon substrate have been measured using ultraviolet photoemission and inverse photoemission spectroscopies in the same UHV chamber. The combination of these two techniques has enabled the direct determination of the oxide energy gaps as well as the offsets of the oxide valence- and conduction-band edges from those of the silicon substrate. These results are supplemented with synchrotron x-ray photoemission spectroscopy measurements allowing further characterization of the oxide composition and the evaluation of the silicon substrate contribution to the spectra. The electron affinity has also been systematically measured on the same samples. We find reasonably good agreement with earlier experiments where assumptions regarding energy-gap values were needed to establish the conduction-band offsets. The systematics of our photoemission and inverse photoemission results on different ultrathin films provide a comprehensive comparison of these related systems.