Using a single-potential-step coelectrodeposition route, Ppy-SiO2 nanocomposite films characterized by a multimodal porous structure were cathodically deposited from ethanolic solutions on oxidizable and nonoxidizable substrates for the first time. The materials produced have an interesting and unique strata-like pore structure along their depth. With the exception of a silica-rich inner region, the nanocomposite films are homogeneous in composition. Because the region closest to the electrode surface is 'Silica-rich, the fabrication of Ppy-SiO2 and Ppy free-standing films become possible using a multistep etching strategy. Such films can be captured on a variety of different supports depending on the application, and they maintain their conductivity when interfaced with an electrode surface. These mesoporous composite films form through a unique mechanism that involves the production of two catalysts, OH- and NO+. Through the process of understanding the reaction mechanism, we highlighted the effect of two simultaneous competing redox reactions occurring at the electrode interface on the morphology of the electrodeposited Ppy nanocomposite films and how solvent can influence the Ppy electropolymerization reaction mechanism and hence control the morphology of the final material. In an ethanolic solvent system, the pyrrole monomers undergo a step-growth polymerization) and particulate-like nanostructurecl films were obtained even upon changing the monomer or acid concentration: In an aqueous-based system, nanowire-like structures were produced, which is consistent with a chain-growth mechanism. Such materials are promising Candidates for a wide range, of applications including electrochemical sensing, energy storage, and catalysis.