An efficient palladium-catalyzed trifluoromethylthiolation of chelation-assisted C–H bonds has been accomplished by employing a readily accessible trifluoromethylthiolating reagent. The reaction tolerates various directing groups and functional groups and allows the access to diverse trifluoromethylthiolated arenes in good yield. A plausible mechanism was proposed based on preliminary mechanistic investigations. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim