Heterogeneous epitaxial growth between semiconductors and metals boosts novel device development and enables various applications. In this work, we have investigated the epitaxial growth of GaAs layers on top of a nanoscale aluminium-transformed AlAs film. The grown GaAs layers are single-crystalline and of high-quality, that has been evidenced by using various material characterization methods and by fabricating their high-electron mobility transistors. We found that an intriguing process named as “arsenidation” of aluminium film plays a key role in the successful epitaxy. Our work opens a window for growing semiconductor/metal hetero-structures for various device applications in the future.