Solid　oxide　carbon　dioxide　electrolyser　may　play　a　key　role　in　transforming　our　global　energy　landscape　into　a　carbon–neutral　energy　cycle.　However,　the　dominant　process　of　oxygen　transfer　at　interfaces　generally　controls　electrode　activity.　This　article　reports　a　generic　method　that　pertains　to　oxygen　transfer　engineering　at　interfaces　so　as　to　enhance　CO2　electrolysis　via　cooperative　control　of　interface　architectures,　materials　compositions　and　materials　functionalities.　The　strong　coupling　of　oxygen　vacancy　with　metal　nanoparticles　significantly　enhances　oxygen　transfer　constants　by　∼　10　times　at　NixCu1-x-La0.2Sr0.8Ti0.9Mn0.1O3+δ　interfaces.　Electrode　activity　therefore　demonstrates　a　strong　dependence　on　oxygen　transfer　at　interface.　It　is　observed　that　the　nanostructured　cathode　could　maintain　exceptionally　high　performance　when　it　works　at　high　temperature　operation　after　500　h　as　well　as　10　redox　cycles.　This　work　provides　an　in-depth　understanding　of　electrode　activity　and　a　general　guidance　of　metal-oxide　interfaces　for　designing　nanostructured　electrodes.　©　2022　Elsevier　B.V.