Metal-organic　frameworks　(MOFs)　with　highly　adjustable　structures　are　an　emerging　family　of　electrocatalysts　in　two-electron　oxygen　reduction　reaction　(2e-ORR)　for　H2O2　production.　However,　the　development　of　MOF-based　2e-ORR　catalysts　with　high　H2O2　selectivity　and　production　rate　remains　challenging.　Herein,　an　elaborate　design　with　fine　control　over　MOFs　at　both　atomic　and　nano-scale　is　demonstrated,　enabling　the　well-known　Zn/Co　bimetallic　zeolite　imidazole　frameworks　(ZnCo-ZIFs)　as　excellent　2e-ORR　electrocatalysts.　Experimental　results　combined　with　density　functional　theory　simulation　have　shown　that　the　atomic　level　control　can　regulate　the　role　of　water　molecules　participating　in　the　ORR　process,　and　the　morphology　control　over　desired　facet　exposure　adjusts　the　coordination　unsaturation　degree　of　active　sites.　The　structural　regulation　at　two　length　scales　leads　to　synchronous　control　over　both　the　kinetics　and　thermodynamics　for　ORR　on　bimetallic　ZIF　catalysts.　The　optimized　ZnCo-ZIF　with　a　Zn/Co　molar　ratio　of　9/1　and　predominant　{001}　facet　exposure　exhibits　a　high　2e-　selectivity　of　∼100%　and　a　H2O2　yield　of　4.35　mol　gcat-1　h-1.　The　findings　pave　a　new　avenue　toward　the　development　of　multivariate　MOFs　as　advanced　2e-ORR　electrocatalysts.　©　2023　American　Chemical　Society.