The first example of 3-position-selective C(sp 2 )-H trifluoromethylation of pyridine rings was established. The C3 trifluoromethylation was achieved by nucleophilic activation of pyridine and quinoline derivatives through hydrosilylation and successive electrophilic trifluoromethylation of the enamine intermediate. This reaction was applicable to perfluoroalkylation at the C3-position of pyridine rings and the late-stage trifluoromethylation of a bioactive molecule. Mechanistic study indicated that the reaction proceeded via the formation of N-silyl enamine and trifluoromethylated enamine intermediates.