Co-based　metal–organic　frameworks　(MOFs)　as　electrocatalysts　for　two-electron　oxygen　reduction　reaction　(2e−　ORR)　are　highly　promising　for　H2O2　production,　but　suffer　from　the　intrinsic　activity-selectivity　trade-off.　Herein,　we　report　a　ZnCo　bimetal-triazole　framework　(ZnCo-MTF)　as　high-efficiency　2e−　ORR　electrocatalysts.　The　experimental　and　theoretical　results　demonstrate　that　the　coordination　between　1,2,3-triazole　and　Co　increases　the　antibonding-orbital　occupancy　on　the　Co−N　bond,　promoting　the　activation　of　Co　center.　Besides,　the　adjacent　Zn−Co　sites　on　1,2,3-triazole　enable　an　asymmetric　＇side-on＇　adsorption　mode　of　O2,　favoring　the　reduction　of　O2　molecules　and　desorption　of　OOH*　intermediate.　By　virtue　of　the　unique　ligand　effect,　the　ZnCo-MTF　exhibits　a　2e−　ORR　selectivity　of　≈100　%,　onset　potential　of　0.614　V　and　H2O2　production　rate　of　5.55　mol　gcat−1　h−1,　superior　to　the　state-of-the-art　zeolite　imidazole　frameworks.　Our　work　paves　the　way　for　the　design　of　2e−　ORR　electrocatalysts　with　desirable　coordination　and　electronic　structure.　©　2023　Wiley-VCH　GmbH.