Various structural as well as chemical properties of ultrathin Al 2 O 3 films prepared on Nb͑110͒/ sapphire͑0001͒ were analyzed. For this purpose, in a first step, 40-nm-thick Nb͑110͒ films are grown epitaxially by sputtering on top of sapphire͑0001͒. The Nb͑110͒ films are (1ϫ1) reconstructed and exhibit the epitaxial relations Nb(110)ʈAl 2 O 3 (0001), Nb͓001͔ʈAl 2 O 3 ͓1 គ 010͔ and equivalents as determined by x-ray diffraction. In a second step, a 1-nm-thick Al film is evaporated on top of the Nb͑110͒ and oxidized ex situ in an oxygen plasma resulting in a polycrystalline Al 2 O 3 film of thickness ϳ1.3 nm. This oxide film was characterized by scanning tunneling microscopy and spectroscopy ͑STS͒ as well as by x-ray photoelectron spectroscopy. Additionally, the ultrathin Al-oxide films were tested as insulators in large area metal-insulator-metal ͑MIM͒ or superconductor-insulator-metal tunneling contacts. According to these experiments, the niobium film underneath is completely protected from oxidation, while the Al film is fully oxidized without pinholes over areas of some mm 2 . The tunneling barrier heights range from 1.0 to 1.5 eV according to MIM tunneling and STS.