In the present work, LDHs-derived Ni–Al nanosheet arrays (NiAl/NA) were successfully synthesized via a one-step hydrothermal method, and applied in the steam-reforming of glycerol reaction for enhanced and stable hydrogen production. The physicochemical properties of catalysts were characterized using various techniques, including XRD, SEM–EDS, XPS, N₂-physisorption, Raman, and TG–DTG. The results indicate that smooth and cross-linked Ni–Al mixed metal oxide nanosheets were orderly and perpendicularly grown on the Ni foam substrate. The SEM line scan characterization reveals the metal concentration gradient from the bottom to the top of nanosheet, which leads to distinctly optimized Ni valence states and an optimized binding strength to oxygen species. Owing to the improved reducibility and more exposed active sites afforded by its array structures, the NiAl/NA catalyst shows enhanced glycerol conversion (83.1%) and a higher H₂ yield (85.4%), as well as longer stability (1000 min), compared to the traditional Ni–Al nanosheet powder. According to the characterization results of spent catalysts and to density functional theory (DFT) calculations, coke deposition is effectively suppressed via array construction, with only 1.25 wt.% of amorphous carbons formed on NiAl/NA catalyst via CO disproportionation.