Films of poly[(R)-(−)-3-(1-pyrrolyl)propyl-N-(3,5-dinitrobenzoyl)-α-phenylglycinate] (polyDNBP) were deposited, using the galvanostatic method, onto indium tin oxide electrodes in the presence of the electrolytes tetrabutylammonium tetrafluoro-borate [(C4H9)4NBF4] or LiClO4. Atomic force microscopy revealed that polyDNBP/(C4H9)4NBF4 films exhibited a grainy morphology with higher roughness and greater superficial area than polyDNBP/LiClO4 films. Moreover, polyDNBP/(C4H9)4NBF4 films exhibited a higher capacitive electrochemical response when characterised in LiClO4 rather than in (C4H9)4NBF4. Since polyDNBP films exhibit both n- and p-doping, they may have considerable potential application as electrodes in type III capacitor assemblies.