The metal-free-catalyzed synthesis of allyl nitriles from C sp 2 -C sp 3 coupling between olefins and azobis was carried out. Key on this work was that the synthesis of allyl nitriles directly using olefin as a starting material was considered to be more efficient and economical than the alkyne, alkynyl carboxylic acid, or cinnamic acid used in previous works. Moreover, in this reaction, iodine served as the sole promoter, azobis served as a cyanation reagent, and N 2 was the only nontoxic byproduct that could avoid the utilization of metal catalysts and virulent nitrile reagents and generation of toxic wastes. With an optimum condition in hand, more than 30 examples of desired products including aromatic and aliphatic nitriles have been synthesized in good to excellent yields. Based on control experiments and literature data, a plausible mechanism of cyanation was proposed.