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Abstract Surfactant-free and low Au loading Cu2O@Au and Au hollow cubes, based on electrodeposited Cu2O cubes as sacrificed templates, were prepared by means of a galvanic replacement reaction (GRR). The electrocatalytical performance of the as-prepared catalysts towards carbon dioxide (CO2) electrochemical reduction was evaluated. The experimental results show that Cu2O@Au catalyst can convert CO2 to carbon monoxide (CO) with a maximum Faradaic efficiency (FE) of ~ 30.1% at the potential of − 1.0 V (vs. RHE) and is about twice the FE of the other catalysts at the same potential. By comparison, such electrocatalytical enhancement is attributed to the metal-oxide interface in Cu2O@Au.