AbstractWith the irradiation of visible light, α‐heteroarylation of aliphatic alcohol was selectively achieved under gentle conditions in the present of iodobenzene dichloride. The Minisci‐type cross‐dehydrogenative coupling reaction was performed in the absence of metal and acid. Readily available primary alcohols and electron‐withdrawing heteroarenes can be applied smoothly. Mechanism studies indicated that the PhICl radical and chlorine radical formed from iodobenzene dichloride were responsible for the selective hydrogen atom abstraction of alcohols.