Two-electron　oxygen　reduction　reaction　(2e(-)　ORR)　offers　a　sustainable　pathway　for　hydrogen　peroxide　production,　yet　its　efficiency　relies　on　cost-effective　electrocatalysts　with　tailored　active　sites.　Herein,　a　hybrid　ZnO@ZnO2-x　nanorod　with　tunable　oxygen　vacancies　(O-v)　in　the　outer-skin　peroxidate　thin　film　was　developed　as　a　neutral　electrocatalyst　for　hydrogen　peroxide　production　through　cation-terminated　facet-engineering　and　surface　amorphous　peroxidation.　The　optimized　ZnO@ZnO2-x　(named　am-ZNR-180-24)　electrocatalyst　with　a　moderate　oxygen　vacancy　concentration　(similar　to　17.9　at.%　from　XPS)　on　{0001}　polar-facets　demonstrates　a　nearly　100　%　selectivity　for　H2O2　generation,　achieving　a　high　production　rate　of　11.63　molg(cat.)(-1)h(-1),　with　ultrahigh　and　stable　Faradaic　efficiency　(＞90　%)　in　a　flow-cell　system,　which　ranks　among　the　highest　levels　of　reported　metal　compounds　electrocatalysts.　Characterizations　and　theoretical　results　unveil　that　O-v　on　the　polar　(002)　plane　modulate　the　Zn　3d-band　center,　optimizing　the　adsorption　of　*OOH　intermediates　to　favor　2e(-)　ORR.