Iron (Fe) nanoparticles and graphite (Gr) with different masses of bismuth trisulfide (Bi₂S₃) were mixed by high-energy ball milling treatment to fabricate the corresponding composite iron anodes Bi₂S₃@Fe-Gr. The hydrogen evolution reaction and iron passivation process on these iron electrodes were investigated in alkaline and neutral solutions. The iron electrode Bi₂S₃-3@Fe-Gr (The additional amount of Bi₂S₃ was 3 mg) revealed the strongest ability to inhibit hydrogen evolution among the iron electrodes of the present investigation, while the Bi₂S₃-6@Fe-Gr electrode (The additional amount of Bi₂S₃ was 6 mg) delivered significant performance in inhibiting anodic passivation. This is because the high-energy ball milling process leads to the well-dispersion of Bi₂S₃ and the changes in the surface of Fe nanoparticles, thereby slowing down the passivation of the iron electrode surface.