treatment, paper bleaching, chemical synthesis and healthcare disinfection. [1][2][3][4] The escalating global H 2 O 2 demand is projected to reach 6000 ktons in 2024. [5] However, the current H 2 O 2 synthesis still exclusively relies on the energy-intensive anthraquinone oxidation reaction. [6] Electrochemical two-electron (2e -) oxygen reduction has emerged as a promising route for scalable H 2 O 2 generation, but the highly competitive 4epathway involved in the oxygen reduction reaction (ORR) process greatly diminishes the energy conversion efficiency of 2e -H 2 O 2 production. [7] As such, development of an electrocatalyst with high tendency toward the 2ereduction of oxygen is essential and urgent. [8] Various noble-metal-based catalysts are highly efficient for 2e -ORR, such as Au-Pd, [9] Pt-Hg alloys, [10] and Pd@Au x Pd 1-x nanocubes. [11] However, the scarcity and high price of such catalysts hinder their largescale applications. Accordingly, it is of critical importance to develop earth-abundant transition metal-based electrocatalysts with superior selectivity for the 2epathway to upgrade modern energy devices.Recently, the carbon-based catalysts through doping heteroatoms demonstrate excellent H 2 O 2 electrosynthesis activity and selectivity. Which provides a strategy for deigning catalysts toward two electron pathway. [12][13][14] Specially, the conductive metal-organic frameworks (MOFs) with well-dispersed metal centers and typical porous structures have been regarded as ideal candidates for H 2 O 2 production. [15] Especially, a two dimensional conductive Ni-based MOFs with special π-conjugated electronic structure are reported to follow a twoelectron pathway with H 2 O 2 as the main ORR products, [16,17] but they still suffers from poor H 2 O 2 selectivity due to the weak adsorption ability of oxygen over Ni nodes. [18,19] The critical knob for electrochemical reducing oxygen into H 2 O 2 or H 2 O heavily depends on the thermodynamical binding strength between the catalytically active sites and the oxygen species or oxo-intermediates during ORR. [20,21] Theoretically, the effective regulation of Ni 3d e g -orbital configurations could, in principle, substantially optimize the adsorption capability of *OOH intermediates over the Ni sites of Ni-based electrocatalysts during ORR. [22,23] Recently, various strategies, including defect Herein, a strategy of synergetic dual-metal-ion centers to boost transitionmetal-based metal organic framework (MOF) alloy nanomaterials as active oxygen reduction reaction (ORR) electrocatalysts for efficient hydrogen peroxide (H 2 O 2 ) generation is proposed. Through a facile one-pot wet chemical method, a series of MOF alloys with unique Ni-M (M-Co, Cu, Zn) synergetic centers are synthesized, where the strong metallic ions 3d-3d synergy can effectively inhibit O 2 cleavage on Ni sites toward a favorable two-electron ORR pathway. Impressively, the well-designed NiZn MOF alloy catalysts show an excellent H 2 O 2 selectivity up to 90% during ORR, evidently outperforming...