α-Sulfenyl ketones are potential precursors which find a variety of applications in organic synthesis. Their typical synthesis requires pre-functionalized starting materials and two to three step synthetic sequences. In addition, the selective pre-functionalization of unsymmetrical ketones is a challenge, which limits the synthesis of the desired sulfenylated ketones. To overcome these disadvantages, a metal-free, convenient one-step strategy for synthesizing α-sulfenyl ketones at ambient temperature via a cross-dehydrogenative coupling (CDC) strategy has been developed with a broad substrate scope. Therefore, this CDC strategy for C–S bond formation is attractive and may find wide applications in organic synthesis.