Advances in multi-electron transfer materials and architectured electrodes are two important strategies for innovations in electrochemical energy storage. We herein report the attainment of both by interfacial electrodeposition of freestanding PPY-PEDOT copolymer films. The composition of the copolymer is verified by FTIR and XPS spectra and the dispersion of PPY and PEDOT is studied by EDX mapping. SEM images show the film has an open porous 3D network microstructure. Electrochemical characterizations show that the copolymer film is an excellent supercapacitor electrode material with high specific capacitance, good power capability and cycle performance. The multi-electron transfer nature of the copolymer, the copolymerization synergistic effects and the unique microstructure are responsible for the improved charge-discharge performances. (C) 2017 The Electrochemical Society. All rights reserved.