Developing　high　active　and　stable　cost-effective　bifunctional　electrocatalysts　for　overall　water　splitting　to　produce　hydrogen　is　of　vital　significance　in　clean　and　sustainable　energy　development.　This　work　has　prepared　a　novel　porous　unreported　MOF　(Ni-DPT)　as　a　precursor　to　successfully　synthesize　a　non-noble　bifunctional　NiCoP/Ni12P5@NF　electrocatalyst　through　doping　strategy　and　interface　engineering.　This　catalyst　is　constructed　by　layered　self-supporting　arrays　with　heterojunction　interface　and　rich　nitrogen-phosphorus　doping.　Structural　characterizations　and　the　density　function　theory　(DFT)　calculations　confirm　that　the　interface　effect　of　NiCoP/Ni12P5　heterojunction　can　regulate　the　electronic　structure　of　the　catalyst　to　optimize　the　Gibbs　free　energy　of　hydrogen　(ΔGH*);　simultaneously,　the　defect-rich　layered　nanoarrays　can　expose　more　active　sites,　shorten　mass　transfer　distance,　and　generate　a　self-supporting　structure　for　in-situ　reinforcing　the　structural　stability.　As　a　result,　this　NiCoP/Ni12P5@NF　catalyst　exhibits　favorable　electrocatalytic　performance,　which　simply　needs　overpotentials　of　100　mV　for　HER　and　310　mV　for　OER,　respectively,　at　a　current　density　of　10　mA·cm−2.　The　anion　exchange　membrane　electrolyzer　assembled　with　this　NiCoP/Ni12P5@NF　as　both　anode　and　cathode　catalysts　can　operate　stably　for　200　h　at　a　current　density　of　100　mA·cm−2　with　an　insignificant　voltage　decrease.　This　work　may　provide　some　inspiration　for　the　further　rational　design　of　inexpensive　non-noble　multifunctional　electrocatalysts　and　electrode　materials　for　water　splitting　to　generate　hydrogen.　©　2024　Elsevier　Inc.