A highly regioselective and atom-efficient strategy for the construction of fused free (NH) heteroarenes through a palladium-catalyzed perfluoroalkyl insertion reaction has been accomplished. This protocol employed multiple iodofluoroalkanes as practical and available perfluoroalkyl sources to provide an operationally simple and versatile route for the synthesis of perfluoroalkylated indoles. Moreover, indoles without the assistance of guide groups were utilized as substrates, achieving C(sp2)-H site-selective functionalization of indoles in yields up to 95%. Furthermore, this protocol was also used for late-stage C2 perfluoroalkylation of bioactive compounds such as auxin, tryptophan, and melatonin analogues.