Phenyl-2-pyridinyl methanol，as a key pharmacological intermediate, was synthesized via an “one-pot three-steps” method with 2-benzylpyridine nitrogen-oxide and trifluoroacetic anhydride as starting materials, which involved tandem acylation, [3,3]-sigmatropic rearrangement and hydrolysis reaction. The reaction conditions were investigated and the optimal conditions were obtained as follows: trifluoroacetic anhydride was as acylating agent in 1.2 equivalent, N, N-diisopropylethylamine (DIPEA) was as base and the mixture was stirred in toluene for 6 h at room temperature. The phenyl-2-pyridinyl methanol was obtained by silica gel column chromatography with the yield of 81.0%, and the structures of all products were confirmed by 1H NMR，13C NMR and HRMS. This reaction firstly achieved the direct transformation from 2-benzylpyridine nitrogen-oxide to phenyl-2-pyridyl methanol in an atomic economic manner.