A practical iodine-catalyzed oxidative functionalization of isoquinolines with methylarenes is developed, which can be triggered by the selected oxidants to produce C1- or N-benzyl-substituted products selectively. This method utilizes readily available isoquinolines and methylarenes as starting materials and proceeds under metal-free conditions with broad substrate scope with respect to methylarenes, avoiding the usage of expensive metal catalysts and generation of halide and metal wastes...