The formation of the CO/S bonds is of great importance in the synthesis of biologically active molecules and functional materials. Herein, a catalyst‐ and transition metal‐free approach enabling the coupling between N ‐tosylhydrazones and (thio)phenols under photoinduced conditions is presented. This strategy exhibits a broad scope of substrates including various N ‐tosylhydrazones and (thio)phenols, thus demonstrating the feasibility of this concept for CO/S bond formation. Unlike the traditional metal‐catalyzed version, the present reaction offers the advantages of high reaction speed, permitting the preparation of products within just one hour at room temperature. Moreover, the gram‐scale synthesis of thioethers and the generation of pharmaceutical intermediates highlight its practical applicability.