The development of high-performance yet cost-effective catalysts for electrochemical synthesis of H2O2 is a great challenge. Here, the amorphous nickel oxide NiOx supported on carbon nanosheets was prepared by the photochemical metal organic deposition method. The evolution of the crystalline structure, microstructure, and 2-electron oxygen reduction reaction (2e-ORR) activity in 0.1 M KOH was systematically investigated. The results reveal that the amorphous NiOx is highly efficient and selective toward 2e-ORR with an onset potential of 0.76 V versus reversible hydrogen electrode (RHE), 91% selectivity, and an electron transfer number of ∼2.2 over a wide potential range of 0.15-0.60 V versus RHE, which is outstanding among the metal oxide-based catalysts for 2e-ORR. Such a performance is closely associated with the mesoporous structure of the carbon nanosheets. Furthermore, the appropriate bonding strength of Ni-OH derived from the amorphous nature is crucial for the high selectivity. The theoretical calculation reveals that the *OOH intermediate prefers to adsorb on the amorphous NiOx-C by the end-on mode, facilitating the 2e-ORR process. The present amorphous NiOx loaded on carbon nanosheets can be promising electrocatalysts for synthesizing H2O2 after the stability issues are well addressed.