A new approach for the synthesis of aryl cyanides through CC cleavage of styrenyl gem-dibromide via an in situ cyanation process by sodium azide in the presence of CuO nanoparticles and simultaneous intermolecular cyanation of an iodoarene by capturing a released CN unit has been achieved. Several diversely substituted aryl/heteroaryl cyanides including a precursor to etravirine, a drug for the treatment of HIV, have been obtained by this procedure. This protocol is unique with regard to cyanation without a cyanide reagent and provides access to two different nitriles in one reaction involving full utilization of CN units.