In summary, we developed a 3-position-selective trifluoromethylation of pyridine rings based on nucleophilic activation via hydrosilylation. A variety of 6-membered heteroaromatic compounds, such as quinolines, benzoquinoline, isoquinoline, and pyridine, were converted to their corresponding trifluoromethylated products. The reaction proceeded with high regioselectivity, and 3-position trifluoromethylated products were obtained as the sole regioisomer. Carbon-halogen bonds, esters, aryl ethers, and silyl ethers were tolerated under the reaction conditions. The reaction was applicable to perfluoroalkylation at the 3-position of the pyridine rings and late-stage trifluoromethylation of the bioactive molecule quinoxyfen. Mechanistic studies revealed that the reaction proceeds via the formation of N-silyl enamine and 1,4-dihydroquinoline intermediates. We hope that this study will provide significant insights into the 3position-selective transformation of pyridine rings.