A series of five‐membered selenium heterocycles was prepared from the reaction of various selenoureas and phenacyl bromides. In the case of 1‐acyl‐3‐arylselenoureas N‐acyl‐1,3‐selenazol‐2(3H)‐imines are formed, whereas the analogous reaction with 3,3‐disubstituted 1‐acylselenoureas affords 5‐acyl‐1,3‐selenazol‐2‐amines. The compounds were characterized by NMR spectroscopy and mass spectrometry. In addition, the proposed structures were unambiguously confirmed by X‐ray diffraction studies.