This paper describes a new type of polypyrrole film instability brought about by electrolytically generated solution species. Specifically, electrolytes containing "aggressive" anions such as chloride in conjunction with hydroxyl ions emanating from the cathode cause the generation of hypochlorite at the corresponding anode in a single-compartment cell. These electrolytically generated species then attack the polypyrrole film causing it to undergo facile dissolution. A variety of techniques, including quartz crystal microgravimetry, potentiometry, UV-visible spectrophotometry, Raman spectroelectrochemistry, and gas chromatography/mass spectrometry, were used to monitor this process. Remarkably enough, this chemical reaction may be turned "off" by maintaining a negative potential at the polypyrrole/electrolyte interface such that the migration of OCl- to the polymer film is inhibited.