Recycling of aluminum metal from scrap materials demands a high processing temperature, which releases several toxic gases to the environment. In contrast, aluminum metal is known as the cleanest and cheapest source for hydrogen production because of its 3+oxidation state and spontaneous exothermic reaction with water molecules. In this work, we report the hydrothermal synthesis of hybrid Cu2S decorated on nickel foam (NF) for direct aluminum fuel cell application. The hybrid structure of the Cu2S nanoflake- and nanosphere-based catalyst distributed on the three-dimensional (3D) skeletal NF is revealed via detailed structural analysis. The Cu2S/NF-8 catalyst electrode exhibits a maximum mass activity of 106.7 mA/mg at an overpotential of 0.8 V (vs Hg/HgO) for a 40 mg Al source. The high mass activity of the optimized Cu2S/NF-8 catalyst electrode is attributed to the hybrid Cu2S structure, which facilitates improved electrocatalytic activity via its point defects and metallic edges. Likewise, the high electrical conductivity, chemical stability, and rapid charge transfer at the electrode with a short diffusion path are because of the arrangements of the hybrid Cu2S on the NF substrate. The stability and real-time performance of the Cu2S/NF-8 catalyst electrode is successfully studied via chronoamperometry in the presence of an Al ball and a scrap aluminum source. The electrode exhibits a capacity retention of ∼60% (for 7000 s; Al ball) and ∼35% (for 100000 s; scrap Al). This proves the Cu2S/NF-8 catalyst electrode as a promising platform for aluminum source-based fuel cell applications. © 2022 American Chemical Society. All rights reserved.