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Hybrid superconductor–semiconductor materials systems are promising candidates for quantum computing applications. Their integration into superconducting electronics has enabled on-demand voltage tunability at millikelvin temperatures. Ge quantum wells have been among the semiconducting platforms interfaced with superconducting Al to realize voltage tunable Josephson junctions. Here, we explore Nb as a superconducting material in direct contact with Ge channels by focusing on the solid-state reactions at the Nb/Ge interfaces. We employ Nb evaporation at cryogenic temperatures (∼100 K) to establish a baseline structure with atomically and chemically abrupt Nb/Ge interfaces. By conducting systematic photoelectron spectroscopy and transport measurements on Nb/Ge samples across varying annealing temperatures, we elucidated the influence of Ge out-diffusion on the ultimate performance of superconducting electronics. This study underlines the need for low-temperature growth to minimize chemical intermixing and band bending at the Nb/Ge interfaces.