Supercapacitors are electrochemical energy storage devices with high power density. However, application of supercapacitors is limited mainly due to their high leakage current. In this work, application of an ultra-thin layer of electrodeposited poly (p-phenylene oxide) (PPO) has been investigated as a blocking layer to reduce the leakage current. The polymer was first deposited on a glassy carbon electrode. The morphology of the film was studied by atomic force microscopy (AFM), and the film thickness was estimated to be ∼1.5 nm by using the electrochemical impedance spectroscopy (EIS) technique. The same deposition method was applied to coat the surface of the activated carbon electrodes of a supercapacitor with PPO. The specific capacitance, the leakage current, and the series resistance were measured in two devices with and without the blocking layer. The results demonstrate that the application of the PPO layer reduced the leakage current by ∼78%. However, the specific capacitance was decreased by ∼56%, when the blocking layer was applied. Due to the lower rate of self-discharge, the suggested approach can be applied to fabricate devices with longer charge storage time.