A direct metal-free amination of arylalkynes has been developed, which proceeds by reaction of the terminal alkyne with the hypervalent iodine reagent PhI(OAc)NTs₂ within a single-step operation. This unprecedented intermolecular C-H to C-N bond conversion provides rapid access to the important class of ynamides. In addition to the title reaction, the related transformation between alkylated alkynes and the iodine(III) reagent is also discussed.