Since the landmark work of Heck, Negishi and Suzuki on Pd-catalyzed crossing coupling reactions, innovative discovery of new reactions forming C-C bonds and constructing functional olefins via nonmetal catalysts remains an imperative area in organic chemistry. Herein, we report a transition-metal-free arylation method of vinyl pinacolboronates with diaryliodonium salts to form C(sp 2 )-C(sp 2 ) bond and provide trans-arylvinylboronates. The resulting vinylboronates can further react with the remaining aryl iodides (generated from diaryliodonium salts) via Suzuki coupling to afford functional olefins, offering an efficient use of aryliodonium salts. Computational mechanistic studies suggest radical-pair pathway of the diaryliodonium salts promoted by the multi-functional wet carbonate.