The effect of hydrogen peroxide on the electrochemical behavior of iron was investigated in perchlorate solutions. Iron showed four distinct behaviors in the perchlorate solutions of pH 3.0. First, the active dissolution regions of Fe with two current waves were observed in the potential range of −0.7 to 0 V (vs. SCE). Second, the stable passivation was found in the potential range between 0 and 0.3 V (vs. SCE). Third, unstable passivation region was observed in the potential range of 0.3 to 1.2 V (vs. SCE). Finally, pitting corrosion was observed at a potential above 1.2 V (vs. SCE). The pH increase stabilized the passivation process of iron, whereas the increase in temperature had a negative influence by enhancing the passivation and pitting behaviors of iron. The presence of hydrogen peroxide at the concentrations below 1.45 mM had an adverse effect on the formation of the passive layer. However, at concentrations above 1.45 mM, hydrogen peroxide affected a beneficial influence on the formation of stable iron oxide layer in the active dissolution region. In addition, regardless of the hydrogen peroxide concentration, the presence of hydrogen peroxide mitigated the pitting corrosion of iron.