A novel method to modify the surfaces of transition metal oxides (MO) film-electrode was proposed in this study. At first, a monolayer of terephthalic acid was covalently bonded to the surfaces of Cu2O films. Then silver (Ag) particles were electrodeposited on the monolayer-grafted films by a potential-step process. The resulting Ag–Cu2O films exhibited improved electrochemical performance as negative electrodes in lithium-ion batteries compared to the original Cu2O films. An increase in electrical contact between Cu2O particles was considered to be responsible for the improvement in the electrochemical properties.