In the presence of a high concentration of weak-acid anions, such as monohydrogenophosphate which confer to a pyrrole aqueous solution a pH around 9, an ultra thin non-conductive overoxidized polypyrrole film is deposited on the electrode under an anodic polarization. In the same experimental conditions, after addition of perchlorate anions (C > 0.5 mM) in the pyrrole solution the electrooxidation of the monomers leads to the synthesis of a superhydrophilic nanostructured conductive polypyrrole film (network of nanofibers or oriented nanowires, 50-120 nm in diameter). The aim of the present paper is to confirm the mechanism that we have previously proposed and so to explain the spontaneous nanostructuration of the electrogenerated polypyrrole films. We have assumed that this templateless formation of nanostructures is notably due to the oxidation of water with production of hydroxyl radicals and nanobubbles of dioxygen. Due to the fact that pyrrole polymerization is associated to the release of protons, we have first verified that the electrode/solution interfacial pH is compatible with the water oxidation potential. For this purpose, during the monomer oxidation the interfacial pH variation has been monitored using a pH electrode having a flat glass membrane which was covered with a Pt grid used as the working electrode. Secondly, the presence of dioxygen nanobubbles has been indirectly confirmed by rotating the working electrode. Indeed rotation of the electrode allows eliminating the nanobubbles present inside the polypyrrole film. For the highest rotation speed tested (94 rad s (1)), a very thin overoxidized film was electrogenerated. Our results are in good agreement with the fact that the nanobubbles protect the PPy film against the action of the hydroxyl radicals which react with the polypyrrole film leading to its overoxidation. (C) 2015 Elsevier Ltd. All rights reserved.