Ferrous iron (Fe(II)) produced by microbial Fe(III) reduction and reactive oxygen species (ROS) generated from aerobic Fe(II) oxidation can mediate iodate (IO3−) reduction and iodide (I−) oxidation, respectively. Nevertheless, how Fe redox cycling under redox fluctuating conditions drives transformation of iodine species remain unclear. In this study, Shewanella oneidensis MR-1 wildtype (WT) and its mutant △dmsEFAB, which lost the ability to enzymatically reduce IO3−, were chosen to conduct ferrihydrite/goethite/nontronite culture experiments under consecutive cycles of anoxic reduction of Fe(III) and re-oxidation of Fe(II) by O2 to reveal the role of Fe redox cycling in the transformation of iodine species. The results showed that both surface-adsorbed and mineral structural Fe(II) chemically reduced IO3−. Chemical IO3− reduction by biogenic Fe(II) was slower than enzymatic IO3− reduction by WT. Compared to △dmsEFAB cultures, WT cultures all showed higher Fe(II) concentrations under anoxic conditions but lower cumulative •OH under oxic conditions, which imply the chemical reaction between I− and ROS. I− oxidation by ROS, however, did not lead to a significant production of IO3− compared with I− formed under anoxic conditions. Consequently, Fe redox cycling successively reduced IO3− to I−, which highlights vital roles of Fe(III)-reducing bacteria in I− formation and mobilization in environments.