AbstractWe have established an effective one‐pot construction of arylcyanmides and o‐halo arylcyanamides under metal‐free conditions with water at room temperature. Here we have used molecular iodine as a desulfurizing agent. During our standardization study, we could find the desired product in good yields using surfactant (1 % TPGS‐750‐M) and additive (NaOH). Library of aryl isothiocyanates readily converted into their respective desired products 2 a–j in 90–97 % yields. Similarly, o‐halo arylisothiocyanates carried out the reaction to give their respective halo cyanamides in good yields. Further, tetrazole compounds have also been constructed from cyanamides through click‐reaction under moderate reaction conditions.