Arsenite removal from aqueous medium is quite challenging as most of the conventional methods fail to exhibit arsenite removal completely. The present article examines the possibility of electrochemical advanced oxidation processes to remove arsenite from water medium. Anodic oxidation and electro‐Fenton processes failed to remove generated arsenate in the system but found effective to oxidize arsenite completely from its initial concentrations of 1 mg/L and 10 mg/L. Arsenite oxidation is mainly due to in‐situ generated hydrogen peroxide and hydroxyl radicals for anodic oxidation and electro‐Fenton processes. However, peroxicoagulation process was found effective for the oxidation of arsenite as well as removal of arsenic in water. Complete removal of arsenic was observed within 30 min of electrolysis time for pH range in between 3 to 11. Overall, peroxicoagulation is an effective way to remove arsenic from aqueous solution.