This work studies the dependence of the electrical conductivity of HClO4 doped polyaniline (PAni) on the potential in an aprotic electrolyte (1M LiClO4 in EC/DMC) and establishes that it possesses a sufficiently high conductivity within a narrow potential range 3.3–3.5V vs. Li/Li+, beyond which its resistance increases sharply. It is shown that PAni, as a component of lithium battery electrodes, could be subjected to stable charge-discharge cycling in the 1.0–4.2V vs. Li/Li+ potential range and that decrease of the lower limit of the potential range below 1.0V could lead to the formation of an SEI layer, which causes the irreversible reduction of PAni electrochemical performance.