In this study, the electrochemical behavior of an Al–air battery is improved by mixing 6‐thioguanine into 4.0 M NaOH electrolyte. The electrochemical performance of the Al electrodes is analyzed using potentiodynamic polarization, potentiostatic oxidation, and electrochemical impedance spectroscopy. The surface morphology of the Al electrodes after discharging for 1,000 s is characterized using scanning electron microscopy coupled with X‐ray elemental mapping for Al, O, C, N, and S. Furthermore, the utilization efficiencies of these samples are also determined. The results show that the corrosion resistance of the Al electrodes initially increases and then decreases with an increase in 6‐thioguanine concentration. The presence of 6‐thioguanine enhances the corrosion resistance to the maximum, with a corrosion current density (Icorr) of 6.170 mA/cm2, and corrosion inhibition efficiency (η) of 36.56%, at 0.5 mM of 6‐thioguanine.