In this work we report a green procedure for the infiltration of a SPEEK solution into a porous carbon electrode resulting in a thin-film cation exchange membrane. The electrodes have been investigated by a morphological point of view, showing the formation of a thin coating infiltrated into the porous carbonaceous matrix, while mechanical peeling of a tape demonstrated the adhesion of the proposed layer. The fabricated electrodes have been analyzed by electrochemical measurement. The 3-electrode cyclic voltammetry measurements allowed to verify the voltage window resulting in an improved negative potential, while the electrochemical impedance spectroscopy showed a reduction of the electrical resistance. The SPEEK electrode was used in a supercapacitor and deeply characterized by electrochemical analysis. The reported findings demonstrate for the first time the possibility to exploit a cation exchange material in thin film configuration for supercapacitor application with improved performance of the device and exclusively involving the use of nontoxic reagents.