A new iron‐facilitated silver‐mediated radical 1,2‐alkylarylation of styrenes with α‐carbonyl alkyl bromides and indoles is described, and two new C−C bonds were generated in a single step through a sequence of intermolecular C(sp3)−Br functionalization and C(sp2)−H functionalization across the alkenes. This method provides an efficient access to alkylated indoles with broad substrate scope and excellent selectivity. Bridging alkene: An intermolecular arene C(sp2)−H functionalization strategy is established for the radical 1,2‐alkylarylation of styrenes with α‐carbonyl alkyl bromides and indoles using iron as the catalyst and silver as the promotor. This method enables the formation of two C−C bonds in a single reaction. acac=acetylacetonate.