Transition　metal　pnictide　catalysts,　especially　Ni-based　nitrides　and　phosphides,　exhibit　superior　activity　and　selectivity　in　anodic　electrocatalysis　compared　to　oxides.　However,　the　mechanisms　underlying　their　enhanced　performance　remain　unclear.　This　study　synthesized　Ni-based　pnictides　and　control　samples　(NiAx,　A　=　O,　N,　P)　on　nickel　nanorod　arrays　(Ni　NRAs)　via　plasma　treatment.　Among　them,　NiNx　showed　optimal　performance　for　glycerol　electrooxidation　(GOR),　achieving　10　and　50　mA∙cm−2　at　1.29　and　1.39　V,　with　a　94.3　%　Faraday　efficiency　for　formate　production.　Mechanism　analysis　revealed　that　nitrogen　coordination　primarily　improves　GOR　performance　by　enabling　an　optimized　oxidative　reconstruction　process　facilitated　by　-NOx　linkages,　which　reduce　the　dehydrogenation　energy　barrier　of　Ni-based　hydroxides,　promoting　the　formation　of　highly　active　and　structurally　ordered　NiOOH　sites;　in　fact,　the　intrinsic　activity　of　NiOOH　was　largely　unaffected　by　N　coordination.　In　contrast,　Ni-POx　and　Ni-O　systems　exhibit　inferior　performance　due　to　less　efficient　reconstruction.　These　results　challenge　the　assumption　that　enhanced　catalytic　activity　arises　solely　from　Ni　sites　coordinated　with　non-oxygen　heteroatoms.　Instead,　this　work　highlights　the　importance　of　oxidative　reconstruction　processes,　providing　insights　into　designing　cost-effective　and　efficient　anodic　catalysts.　©　2025