Overcoming the difficulty in the precise definition of the metal phase of metal−Si heterostructures is among the key prerequisites to enable reproducible next-generation nanoelectronic, optoelectronic, and quantum devices. Here, we report on the formation of monolithic Al−Si heterostructures obtained from both bottom-up and top-down fabricated Si nanostructures and Al contacts. This is enabled by a thermally induced Al−Si exchange reaction, which forms abrupt and void-free metal−semiconductor interfaces in contrast to their bulk counterparts. The selective and controllable transformation of Si NWs into Al provides a nanodevice fabrication platform with high-quality monolithic and single-crystalline Al contacts, revealing resistivities as low as ρ = (6.31 ± 1.17) × 10 −8 Ω m and breakdown current densities of J max = (1 ± 0.13) × 10 12 Ω m −2 . Combining transmission electron microscopy and energy-dispersive X-ray spectroscopy confirmed the composition as well as the crystalline nature of the presented Al−Si−Al heterostructures, with no intermetallic phases formed during the exchange process in contrast to state-of-the-art metal silicides. The thereof formed single-element Al contacts explain the robustness and reproducibility of the junctions. Detailed and systematic electrical characterizations carried out on back-and top-gated heterostructure devices revealed symmetric effective Schottky barriers for electrons and holes. Most importantly, fulfilling compatibility with modern complementary metal−oxide semiconductor fabrication, the proposed thermally induced Al−Si exchange reaction may give rise to the development of nextgeneration reconfigurable electronics relying on reproducible nanojunctions.