Herein, we reveal for the first time a comprehensive mechanism of poorly investigated electrochemical decomposition of CH3NH3PbI3 using a set of microscopy techniques (optical, AFM, PL) and ToF-SIMS. We demonstrate that applied electric bias induces the oxidation of I- to I2, which remains trapped in the film in the form of polyiodides, and hence, the process can be conceivably reversed by reduction. On the contrary, reduction of organic methylammonium cation produces volatile products, which leave the film and thus make the degradation irreversible. Our results lead to a paradigm change when considering design principles for improving the stability of complex lead halide materials as those featuring organic cations rather than halide anions as the most electric field-sensitive components. Suppressing the electrochemical degradation of complex lead halides represents a crucial challenge, which should be addressed in order to bring the operational stability of perovskite photovoltaics to commercially interesting benchmarks.