of the nitrogen atom allows milder single-electron oxidation for the respective radical cation generation (Scheme 2a). Moreover, the resultant ynamide radical cation still features a high reactivity, but it is tempered by a keteniminium radical resonance contributor which provides enhanced stability and can also act as an efficient directing group for controllable selective transformations. Considering the electrophilicity nature of radical cation, the facile access to ynamide alkyne radical cations could provide a basis to develop a general system for a range of heteroatom nucleophiles reacting with ynamides. Herein, we report the direct intramolecular hydroamination of ynamides with nitrogen heteroaromatic nucleophiles via photoredox catalyzed radical cation generation (Scheme 2b). This transformation delivers a facile photoredox catalyzed approach for the synthesis of a variety of α-heteroarene substituted enamides, and notably, it provides a new reactivity profile that complements traditional acid or transition metal catalyzed ynamide reactions.