While the properties of the non-(1 0 0) Ge surface become more important with the scaling down of Ge-based transistor devices, the stability and electronic properties of the interface between non-(1 0 0) Ge and amorphous GeO 2 (a-GeO 2 ) compared to those of Ge(1 0 0) and a-GeO 2 are still not well known. In this study, first-principles calculations were performed to systematically study the atomic and electronic structures of Ge/a-GeO 2 interfaces with various surface orientations of Ge. The study shows that the Ge(1 1 1)/a-GeO 2 and Ge(1 0 0)/a-GeO 2 interfaces have the lowest and highest interface energies, respectively. The stability of the Ge/a-GeO 2 interface is governed by the interfacial bond density and the minimization of the dangling bonds. We find that the interface region, composed of the Ge suboxides, dominates the electronic structures of the Ge/a-GeO 2 . The Ge atoms with uncompensated dangling bonds result in various trap states within the band gap of Ge, which is related to the charge neutrality level of the Ge defect. The band offsets between Ge and a-GeO 2 show little dependence on the original Ge orientation.