Activation of the carbon– halogen bonds in aryl halides is a key step in transition-metal-free cross-coupling reactions. In this paper, a new and efficient radical initiation system for the activation of iodoarenes to produce aryl radicals was discovered, which employs the combination of N-methylanilines and tBuOK. This radical initiation system is robust and versatile, enabling various types of aryl-radical-related reactions.