Due　to　the　multiclass　complex　processes　in　the　oxygen　evolution　reaction　(OER)　by　Ni-based　double　hydroxides　(DHs)　electrocatalysts,　it　is　necessary　to　seek　a　comprehensive　assessment　to　uncover　the　electrochemical　nature.　Here,　Ni0.8M0.2　DHs　and　Ni0.7M0.3　DHs　nanowires　(M　=　Zn,　Co,　Fe,　Cu)　were　prepared　by　a　hydrothermal　method.　As　the　intrinsic　chemical　property,　metal　ion　electronegativity　(MIE)　as　the　descriptor,　the　structure–activity　relationship　between　MIE　and　OER　reaction　intermediates＇　adsorption　and　desorption　capacity　was　researched　by　the　electrochemical　impedance　analysis.　At　the　top　of　the　volcano　trend　(MIE　=　1.39,　Ni0.8Co0.2　DHs),　it　is　screened　and　exhibits　the　lowest　interfacial　charge　transfer　resistance　and　the　adsorption　and　desorption　resistance　of　intermediates.　This　work　provides　a　cost-effective　method　based　on　the　theory　of　electronegativity　equilibrium　for　the　precise　screening　and　design　of　high-active　OER　electrocatalysts.　©　2022　Elsevier　B.V.