We have investigated the structural and band alignment properties of nanoscale titanium dioxide (TiO2) thin films deposited on epitaxial crystallographic oriented Ge layers grown on (100), (110), and (111) A GaAs substrates by molecular beam epitaxy. The TiO2 thin films deposited at low temperature by physical vapor deposition were found to be amorphous in nature, and high-resolution transmission electron microscopy confirmed a sharp heterointerface between the TiO2 thin film and the epitaxially grown Ge with no traceable interfacial layer. A comprehensive assessment on the effect of substrate orientation on the band alignment at the TiO2/Ge heterointerface is presented by utilizing x-ray photoelectron spectroscopy and spectroscopic ellipsometry. A band-gap of 3.33 +/- 0.02 eV was determined for the amorphous TiO2 thin film from the Tauc plot. Irrespective of the crystallographic orientation of the epitaxial Ge layer, a sufficient valence band-offset of greater than 2 eV was obtained at the TiO2/Ge heterointerface while the corresponding conduction band-offsets for the aforementioned TiO2/Ge system were found to be smaller than 1 eV. A comparative assessment on the effect of Ge substrate orientation revealed a valence band-offset relation of Delta E-V(100)> Delta E-V(111)> Delta E-V(110) and a conduction band-offset relation of Delta E-C(110) > Delta E-C(111)> Delta E-C(100). These band-offset parameters are of critical importance and will provide key insight for the design and performance analysis of TiO2 for potential high-k dielectric integration and for future metal-insulator-semiconductor contact applications with next generation of Ge based metal-oxide field-effect transistors. (C) 2014 AIP Publishing LLC.