A novel transition‐metal‐free regioselective allylic C−H thiolation of alkenes has been achieved by cross‐dehydrogenative coupling strategy. The present protocol realizes efficient and highly regio‐ and stereo‐selective functionalization of allylic C−H bonds under metal‐free conditions, leading to a series of allylic thioethers in good to excellent yields. Moreover, this work features mild reaction conditions, high step‐ and atom‐economy and good functional group tolerance.