Owing to increased specific surface area and catalytic 'hot spots', nanoporous nickel film (NPNF) have presented an efficiency performance for hydrazine electrocatalysis. NPNF samples were fabricated by dealloying Ni-Al precursor alloys synthesized by magnetron co-sputtering on Ni foils. It was observed that both continuous ligaments and pore channels of the NPNF electrodes with a size of about 38 nm, enabled the electrode to electrocatalyze the hydrazine decomposition with high efficiency at a potential of 0.32 V vs. RHE. We also explored the molecular mechanism of the electrocatalytic decomposition of hydrazine on Ni (111) surface by DFT computations, ideally corresponding to our experimental results. Based on the observations, nanoporous Ni have overthrown the cognition of monometallic Ni for inefficient hydrazine decomposition, improving significantly the technology for hydrogen generation and energy storage. (C) 2019 Elsevier Ltd. All rights reserved.