A one-pot trifluoromethylthiolation-iodination of arynes with trifluoromethylthiosilver (AgSCF3) and 1-iodophenylacetylene is described. This protocol allows rapid construction of o-trifluoromethylthiolated arene building blocks in moderate yields. These products were found to be excellent precursors for Yagupolskii-Umemoto-type electrophilic trifluoromethylation reagents.