Details of the growth properties of polyaniline (PA) have been studied employing electrochemical techniques (potential cycling method) and the results are reported. The electrochemical growth may be characterized as autocatalytic, and the growth rate is first order in aniline concentration. The growth rate is also dependent on the amount of PA film on the electrode as well as the number of potential cycles. The highest oxidized PA, attacked by an aniline molecule, grows to a longer chain, and a net reduction of the PA film upon aniline addition would render the film conducting. This mechanism explains why the film continues to grow at potentials where only passivating behavior would be predicted. In addition, the growth was divided into regions of well‐defined and poorly defined (amorphous) phases; at longer oxidation times during growth, side reactions seem to play more important roles compared to the earlier phase of the growth process.