Structural and band alignment properties of atomic layer Al2O3 oxide film deposited on crystallographically oriented epitaxial Ge grown in-situ on (100), (110), and (111)A GaAs substrates using two separate molecular beam epitaxy chambers were investigated using cross-sectional transmission microscopy (TEM) and x-ray photoelectron spectroscopy (XPS). High-resolution triple axis x-ray measurement demonstrated pseudomorphic and high-quality Ge epitaxial layer on crystallographically oriented GaAs substrates. The cross-sectional TEM exhibited a sharp interface between the Ge epilayer and each orientation of the GaAs substrate as well as the Al2O3 film and the Ge epilayer. The extracted valence band offset, ΔEv, values of Al2O3 relative to (100), (110), and (111) Ge orientations using XPS measurement were 3.17 eV, 3.34 eV, and 3.10 eV, respectively. Using XPS data, variations in ΔEv related to the crystallographic orientation were ΔEV(110)Ge>ΔEV(100)Ge≥ΔEV(111)Ge and the conduction band offset, ΔEc, related to the crystallographic orientation was ΔEc(111)Ge>ΔEc(110)Ge>ΔEc(100)Ge using the measured ΔEv, bandgap of Al2O3 in each orientation, and well-known Ge bandgap of 0.67 eV. These band offset parameters are important for future application of Ge-based p- and n-channel metal-oxide field-effect transistor design.