Abstract：P-(trifluoromethoxy)-N-hydroxyethyl-benzenamine (3) was selectively synthesised using p-(trifluoromethoxy)-benzenamine (1) as the raw material . The product was obtained by the route during amidation with chloroethyl chloroformate，then hydrolyzed and rearrangement in NaOH aqueous solution，the structure of products were confirmed by 1H NMR，13C NMR，Ms and IR．Factors on yield of products were studied，it was found that the yield of 3 can reach 93.7% under the optimal reaction condition of n(NaOH)：n(amide) with 5:1 at 50℃ for 7h in dioxane ． Keywords：p-(trifluoromethoxy)-N- hydroxyethyl-benzenamine；p-(trifluoromethoxy)-benzenamine；chloroethyl chloroformate；synthesis Foundation item：Natural Science Foundation of China(20905057)