Enhancing　electrocatalytic　water　splitting　performance　by　modulating　the　intrinsic　electronic　structure　is　of　great　importance.　Here,　porous　bimetallic　oxide　and　chalcogenide　nanosheets　grown　on　carbon　paper　denoted　as　NiCo2X4/CP　(X　=　O,　S,　and　Se)　are　prepared　to　demonstrate　how　the　anion　components　affect　the　electronic　structures　and　thereby　disclose　the　correlation　between　their　intermediates　interaction　and　catalytic　activities.　The　experimental　characterization　and　theoretical　calculation　demonstrate　that　Se　and　S　substitution　can　promote　the　ratio　of　Co3+/Co2+　and　thereby　modulate　the　electronic　structure　accompanied　with　the　upshift　of　d　band　centers,　which　not　only　enhance　the　inner　conductivity　but　also　regulate　the　interaction　between　the　catalyst　surface　and　intermediates,　especially　for　the　adsorption　of　absorbed　H　and　hydroperoxy　intermediates　towards　respective　hydrogen　evolution　reaction　(HER)　and　oxygen　evolution　reaction　(OER).　As　a　result,　a　full　alkaline　electrolyzer　using　NiCo2Se4/CP　and　NiCo2S4/CP　as　cathode　and　anode　delivers　a　low　voltage　of　1.51　V　at　10　mAcm(-2),　which　is　comparable　even　superior　to　most　transition　metal-based　electrolyzers.