Abstract This article reports the synthesis of alpha‐hydroxy‐beta‐seleno amides containing intramolecular hydrogen bonds by selective oxyselenization and selective double bond cleavage reactions of enamine amides with diaryl diselenides under visible light irradiation. This protocol proceeds well to provide the 30 desired products with yields of 37 %–80 % using the 12 W blue LED as light source under room temperature conditions. Moreover, diaryl diselenides plays a dual role as a substrate and a photoactive reagent, as well as oxygen in the air participates in the reaction, thus avoiding the extra addition of environmentally unfriendly photoctalysts and oxidants.