A new O-benzylation reagent, benzyl N-phenyl-2,2,2-trifluoroacetimidate, has been developed. It even reacts with sterically hindered alcohols and base-sensitive hydroxy esters to afford the corresponding benzyl ethers catalyzed by TMSOTf in 1,4-dioxane. This reagent was more stable than benzyl 2,2,2-trichloroacetimidate, a known benzylation reagent.