Structured nickel catalysts for sodium borohydride hydrolysis (SBH) were synthesized by surface modification of nickel foam. The fabrication process consisted of i) nickel aluminization, ii) post-annealing, and iii) selective aluminum leaching. Through low-temperature chemical alloying, nickel was aluminized at 400 °C, and a 0.5 μm-thick NiAl₃ alloy outer-layer was formed. While discontinuing the influx of the aluminum source, post-annealing was conducted to transform the NiAl₃ outer-layer into different Ni–Al alloys, such as NiAl₃ on Ni₂Al₃, Ni₂Al₃ on NiAl, and NiAl on Ni₃Al at 400, 500, and 600 °C, respectively. After the selective aluminum leaching, the surface treatment increased the surface area by factors of 2.2–77.1, leading to a significant enhancement of activity in SBH hydrolysis. Additionally, the catalyst undergoing post-annealing at 400 °C achieved superior performance in both initial activity and durability, due to the adhesion layer of Ni₂Al₃ formed between the outermost catalytic layer and the nickel substrate. Finally, continuous SBH-based hydrogen generation using the catalyst with post-annealing at 400 °C was achieved and the as-developed nickel catalyst produced hydrogen at a rate of up to 400 ± 27 sccm/g_catalyst while exhibiting excellent durability for 3 h.