Abstract: | Visible light‐mediated radical alkenylation of benzylsulfonium salts was achieved by means of fac‐Ir(ppy)3 as a photocatalyst, giving allylbenzenes as products. A variety of functional groups, such as halogen, ester, and cyano, were well tolerated in this transformation. Starting benzylsulfonium salts could be readily prepared from benzyl alcohols by an acid‐mediated substitution, increasing the synthetic utility of this transformation. |