AbstractProducing sp³‐hybridized carbon‐enriched molecules is of particular interest due to their high success rate in clinical trials. The installation of aliphatic chains onto aromatic scaffolds was accomplished by nickel‐catalyzed C(sp²)−C(sp³) cross‐electrophile coupling with arylsulfonium salts. Thus, simple non‐prefunctionalized arenes could be alkylated through the formation of aryldibenzothiophenium salts. The reaction employs an electrochemical approach to avoid potentially hazardous chemical redox agents, and importantly, the one‐pot alkylation proved also viable, highlighting the robustness of our approach.