Cuprous oxide (Cu2O) thin film was decorated with copper metal (Cu) by the simple electrochemical deposition method. This study was motivated to improve the role of Cu as a co-catalyst due to the narrow band gap energy of known photocatalyst Cu2O. Cu was electrodeposited on Cu2O thin film with a substrate of indium tin oxide (ITO) at a voltage of -0.3V and a temperature of 60 °C in CuSO4 (pH 10) under a magnetic stirrer. The structure, phase, and morphology of Cu2O/Cu were characterised by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The electrocatalytic performance of Cu2O/Cu was recorded using linear sweep voltammetry and electrochemical impedance spectroscopy. XRD and SEM results show Cu was successfully deposited covering Cu2O. The current density of Cu2O/Cu increased by 2.7041 mA/cm2 confirming the lower charge current resistance of 2.48 kΩ. The Cu-decorated Cu2O demonstrated an improved photocatalytic activity, as shown by the increase of MB degradation from 46.33% to 50.87%. It was believed from characterisations that Cu deposition leads to more dense carriers and charge transfer, hence higher photocatalytic activity towards MB degradation than bare Cu2O thin film.