Abstract N‐trifluoromethylsuccinimide (NTFS) as a new trifluoromethylation reagent was designed and prepared via Ag−CF 3 , and applied to the direct trifluoromethylation of free aniline, and a series of trifluoromethyl products were obtained with good yields. The practicability of the protocol was verified by a gram‐level experiment and the synthesis of the antiasthmatic drug Mabuterol. In addition, a possible radical mechanism was proposed and verified by related experiments. The protocol provided a new solution for C−H trifluoromethylation of free anilines.