Pretreatment of arsenite (As(III)) to arsenate (As(V)) is crucial in remediation of As(III)-contaminated waterbodies. Hydroxyl or sulfate radicals-based advanced oxidation processes are effective; however, the efficiency becomes low as radicals can be quenched by coexisting matters besides As(III). Both I − and As(III) coexist in several types of contaminated water such as shale gas flowback water. Herein, we proposed using H 2 O 2 to react with I − so as to generate reactive iodine species (RIS) for effective oxidation of As(III). The presence of commonly existing anions, methanol, tert-butanol, 2-propanol, formic acid, humic acid, phenol, and benzoquinone did not affect the oxidation performance. Chromate, Cu 2+ or divalent/trivalent irons would enhance the oxidation. Only hydroquinone (>0.3 mM) had an inhibition effect on the oxidation. Unlike peroxymonosulfate and peroxydisulfate that are reactive to Cl − or Br − , H 2 O 2 only showed a solely selective reactivity for the I − to form the RIS. Our experimental and kinetic simulation results confirmed the most significant reaction pathway and suggested that I 2 and I 3 − were the main responsible intermediates. Our study demonstrated that the RIS possessed a higher selectivity to As(III) compared with other coexisting matters. Therefore, the application of RIS is very promising in the redox conversion mediation.