Electrosynthesis of selenylated‐oxazolone derivatives via cascade selenylation/cyclization of ynamides was disclosed. A series of diaryl diselenides, dialkyl diselenides, and heteroaryl‐substituted ynamides was tolerated in this protocol and delivered 4‐selenyloxazolones in 28‐83% yield. The scale‐up reaction and the oxidation of selenylated‐oxazolones was performed to showcase the practicability of this method. Furthermore, mechanistic experiments indicated that a cationic pathway instead of aradical pathway was probably involved.