Recent Advances in Radical‐Initiated Trifluoroacetylations

In recent years, radical‐mediated trifluoroacetylation has emerged as a straightforward and powerful tool for installing the trifluoroacetyl group into diverse organic molecules. This review systematically summarizes the latest advances in radical‐initiated trifluoroacetylation transformations. The strategies are classified by four types of trifluoroacetyl precursors: ethyl trifluoropyruvate, trifluoroacetic anhydride, β ‐fluorinated organosilicon reagents, and cyclic CF ₃ ‐pyruvate acetals. Mechanistic pathways are carefully analyzed. Reaction conditions, substrate scopes, and synthetic applications are fully discussed to show the generality and superiority of each protocol. Current challenges and future directions are highlighted to inspire more efficient, practical, and sustainable trifluoroacetylation methods. This review provides the first comprehensive summary of radical trifluoroacetylation and serves as a reference for designing novel transformations.