Metal nanowires show promise in a broad range of applications and can be fabricated via a number of methods, such as vapor–liquid–solid process and template-based electrodeposition. However, the synthesis of Al nanowires (NWs) is still challenging from the stable alumina substrate. In this work, the Ni-catalyzed fabrication of Al NWs has been realized using various Al₂O₃ substrates. The growth dynamics of Al NWs on Ni/Al₂O₃ was studied using in situ transmission electron microscopy (TEM). The effect of alumina structures, compositions, and growth temperature were investigated. The growth of Al NWs correlates with the Na addition to the alumina support. Since no eutectic mixture of nickel aluminide was formed, a mechanism of Ni-catalyzed reduction of Al₂O₃ for Al NWs growth has been proposed instead of the vapor–liquid–solid mechanism. The key insights reported here are not restricted to Ni-catalyzed Al NWs growth but can be extended to understanding the dynamic change and catalytic performance of Ni/Al₂O₃ under working conditions.