Many trifluoromethoxylation approaches often proposed nucleophilic Ag I OCF 3 as a key intermediate. However, the structure of this intermediate remains elusive. Herein, the thermally stable, light-insensitive nucleophilic trifluoromethoxylating reagent [Ag(PPh t Bu 2 )(OCF 3 )] (1) was prepared and fully characterized. Reagent 1 reacted with a variety of alkyl electrophiles including benzyl bromodes/chlorides, primary alkyl bromides/ iodides/triflates/nosylates, and secondary alkyl bromides/triflates/nosylates in good to excellent yields. Mechanistic investigation by reaction with three enantioenriched secondary alkyl electrophiles suggested that these reactions proceed via an S N 2 pathway, which is consistent with our original mechanistic hypothesis.