Herein, catalytic difunctionalization of vinyl arenes is reported using iron salt as a catalyst without ligands. A series of substituted alkylboronic acid esters was obtained as a single regioisomer from vinyl arenes at 50 °C. This multicomponent protocol enabled the formation of C–C and C–B bonds to produce boroalkylated products in a single process. A non‐radical pathway is proposed for the reaction in contrast to the radical pathways of iron‐catalyzed hydroalkylation reactions. The organoboron compounds generated from this reaction were further utilized for diverse functional group conversions.