Free-standing polypyrrole films, being the metal-polymer contact located several millimeters outside the electrolyte, give stationary closed coulovoltammetric (charge/potential) loop responses to consecutive potential sweeps from -2.50 V to 0.65 V in aqueous solutions. The continuous and closed charge evolution corroborates the presence of reversible film reactions (electroactivity), together high electronic and ionic conductivities in the full potential range. The closed charge loop demonstrates that the irreversible hydrogen evolution is fully inhibited from aqueous solutions of different salts up to -2.5 V vs Ag/AgCl. The morphology of the closed charge loops shows abrupt slope changes corresponding to the four basic components of the structural electrochemistry for a 3D electroactive gel: reduction-shrinking, reduction-compaction, oxidation-relaxation, and oxidation-swelling. Freestanding films of conducting polymers behave as 3D gel electrodes (reactors) at the chain level, where reversible electrochemical reactions drive structural conformational and macroscopic (volume variation) changes. Very slow hydrogen evolution is revealed by coulovoltammetric responses at more cathodic potentials than -1.1 V from strong acid solutions, or in neutral salts self-supported blend films of polypyrrole with large organic acids. Conducting polymers overcome graphite, mercury, lead, diamond, or carbon electrodes as hydrogen inhibitors, and can compete with them for some electro-analytical and electrochemical applications in aqueous solutions.