Here we report the preparation of primary α‐ketoamides via a highly efficient molecular iodine‐mediated oxidative amidation of aryl methyl ketones with ammonium carbamodithioate. A self‐sequenced iodination/nucleophilic substitution/Kornblum oxidation/amidation mechanism was proposed. In this mechanism, α‐thiocyanatoacetophenone is the key intermediate.