We fabricated a nanostructured brush by carrying out Ni deposition on a through-channel anodic aluminum oxide (AAO) template, followed by removal of the AAO skeleton. The AAO was prepared by a two-step anodization process resulting in pore diameter and thickness of 350 nm and 40 μm, respectively. Subsequently, the AAO underwent an electroless deposition involving sensitization, activation, and Ni plating, in conjunction with polyethylene glycol used as the inhibitor to prevent premature closing of pore opening. After deliberate control in relevant parameters, we obtained a conformal Ni overcoat along every pore channel leading to a reduced average pore diameter of 78 nm. Afterward, the sample was immersed in a KOH solution to remove the AAO structure, forming freestanding Ni tubules in a brush configuration. The nanostructured brush revealed considerable enhancement for hydrogen evolution reaction in both current-potential polarization and galvanostatic measurements, which were attributed to the increment in apparent surface area.