The Pd‐catalyzed vinylation reactions of aryl iodides using 1,2‐dibromoethane is developed for the synthesis of styrenes and stilbenes. In these reactions, vinyl bromide is generated from 1,2‐dibromoethane and then undergoes reductive cross‐coupling with aryl iodides, affording styrene products. Under slightly modified reaction conditions, styrenes can continue reacting with vinyl bromide to form <i>E</i>‐stilbenes, which provides a one‐pot synthetic method for stilbenes. Alcohols, including iso‐propanol and methanol, are employed as the reductant in these reductive cross‐coupling reactions.