 Highlight CU species with tunable loading supported on end-oaked TO2-C were successfully fabricated utilizing MOFs at CUPC precursors via the pre-anchor and post-pyrolysis strategy. CU species with tunable loading supported on end-oaked TO2-C were successfully fabricated utilizing MOFs at CUPC precursors via the pre-anchor and post-pyrolysis strategy. Restructured CUN4 and CU4 performed the highest NH3 yield, 88.2 mole H-1-Cata-1, and FE, 94.3%, at minus 0.75 V due to optimal adsorption of NO3- and rapid conversion of the key intermediates. This article was authored by Shwayong Ji, Kusan, Jikoo and Lu, and others.