Generation of 3-haloarynes from o-iodoaryl triflate-type precursors is reported. The method enables the generation of 3-fluorobenzyne with significantly high electrophilicity at -78 degrees C, allowing the formation of a three-component-coupled product between 3-fluorobenzyne, tetrahydrofuran that is used as a solvent, and a thiol. The ready availability of the precursors and the orthogonality in the conditions for generating arynes from o-silylaryl triflate-type precursors also enhance the synthetic utility of 3-haloaryne intermediates, rendering a diverse range of aromatic compounds easily accessible.