The　slow　kinetics　of　water　dissociation　on　electrocatalysts　lacking　platinum　hinders　the　advancement　of　cost-effective　hydrogen　production　via　alkaline　water　electrolysis.　Herein,　a　hierarchically　peach-flower-shaped　electrocatalyst　consisting　of　copper-restructured　cobalt–nickel/cobalt–nickel　oxide　heterostructure　anchored　on　copper　nanowires　(Cu-CoNiO/CoNi@Cu　NWs)　is　developed　for　efficient　hydrogen　evolution　reaction　(HER).　Benefiting　from　the　optimized　electronic　configuration　and　geometric　structure,　this　Cu-CoNiO/CoNi@Cu　NWs　catalyst　performs　an　outstanding　alkaline　HER　activity　of　29　mV　at　10　mA　cm−2　and　98　mV　at　100　mA　cm−2,　which　is　comparable　with　the　state-of-the-art　Pt/C　catalyst　(26　mV　at　10　mA　cm−2　and　117　mV　at　100　mA　cm−2).　Our　findings　rank　among　the　topmost　catalytic　efficiencies　when　compared　to　all　previously　reported　non-noble　metal　catalysts　and　numerous　noble　metal　catalysts.　The　combined　experimental　exploration　and　theoretical　studies　reveal　that　the　incorporation　of　Cu　dopant　into　CoNiO/CoNi　heterostructure　enhances　electron　transfer　from　metal　atoms　to　O　atom,　leading　to　the　formation　of　the　polarized　electric　field　to　accelerate　water　dissociation　and　H　evolution,　eventually　facilitating　the　overall　alkaline　HER　process.　The　boosted　electron　exchange　and　mass　transportation　deriving　from　the　introduction　of　Cu　NWs　and　hierarchically　peach-flower-shaped　nanostructure　further　reinforce　the　HER　activity　of　the　Cu-CoNiO/CoNi　catalyst.　©　2024　Elsevier　Ltd