Multi-phase interfaces are promising for surmounting the energy barriers of electrochemical CO reduction involving multiple electron transfer steps, but challenges still remain in constructing interfacial micro-structures and unraveling their dynamic changes and working mechanism. Herein, highly active Ag/Cu/CuO heterostructures are electrochemically restructured from Ag-incorporating HKUST-1, a Cu-based metal-organic framework (MOF), and accomplish efficient CO-to-CH conversion with a high faradaic efficiency (57.2% at -1.3 V RHE) and satisfactory stability in flow cells, performing among the best of recently reported MOFs and their derivatives. The combination of / characterizations and theoretical calculations reveals that Ag plays a crucial role in stabilizing Cu(i) and increasing the CO surface coverage, while the active Cu/CuO interfaces significantly reduce the energy barrier of C-C coupling toward the boosted ethylene production. This work not only proves MOFs as feasible precursors to derive efficient electrocatalysts on site, but also provides in-depth understanding on the working interfaces at an atomic level.