The urgent need for power transmission is the reason for leading research on the safer operation of high‐voltage cables. These high‐voltage cables are emerging as an efficient technology for underground power transmission. However, the electrochemical corrosion of aluminium (Al) metal sheaths in these cables is a common and challenging degradation process. Herein, the corrosion mechanisms and electrochemical analysis are investigated by using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), electrochemical impedance spectroscopy (EIS) and laboratory‐designed electrochemical characterisation techniques. In the corrosion experiments, the authors evaluated the corrosion rate by measuring the release rate of hydrogen gas and explored the different roles of sodium polyacrylate (NaPA) during the corrosion process. It is found that the complexation reactions between NaPA and Al inhibited corrosion while increased the resistance of the buffer layer. The proposed mechanisms of corrosion in this study can improve the lifespan and sustainability of high‐voltage power transmission.