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This work deals with electroactive conducting polymers (ECPs) used as a complementary component on purely capacitive silicon nanowires protected by a 3 nm alumina layer. Accordingly, in this work, we use a fast and simple deposition method to create a pseudocapacitive material based on the electropolymerization in aqueous micellar media (SDS and SDBS 0.01 M) of hydroxymethyl-EDOT (EDOT-OH) onto 3 nm alumina-coated silicon nanowires (Al3@SiNWs). The composite material displays remarkable capacitive behavior with a specific capacitance of 4.75 mF·cm−2 at a current density of 19 µA·cm−2 in aqueous Na2SO4 electrolyte. [ABSTRACT FROM AUTHOR]