Ynamides/arylynamines are challenging substrates for oxyacetoxylation, especially due to various reactive sites of the N‐heteroaryl ring. Herein, we report a metal‐free PhI(OAc)2‐mediated oxyacetoxylation of arylynamines/ynamides to provide α‐acetoxyl amides in good to excellent yields. The transformation completes in a short time to afford solely the product in a highly regio‐ and chemo‐selective manner through β‐iodo keteneiminium intermediate, without functionalising the N‐heteroaryl moiety. A metal‐free PhI(OAc)2‐mediated oxyacetoxylation of arylynamines and ynamides to provide α‐acetoxyl amides highly regio‐ and chemoselectively in good to excellent yields, leaving the N‐heteroaryl rings intact, is reported.