A novel avenue of C-O bond construction was facilely achieved via Selectfluor-induced oxygenation of C(sp2)-H bonds of N-substituted anilines by reacting with N-hydroxyphthalimide or N-hydroxymaleimide without any metal catalyst. A variety of N-aryloxyimide derivatives were prepared from N-acyl or sulfonyl anilines in moderate to excellent yields with good functional-group tolerance under mild conditions, which are of great interest in the field of phenol or benzofuran derivative synthesis. Besides, the method is effective on the gram scale, which highlights the practicality of this transformation.