Palladium-catalyzed regioselective allylic amination of the α-trifluoromethyl group-substituted allyl acetate has been accomplished using Pd(OAc) 2 /DPPE and [Pd(π-allyl)(cod)]BF 4 /DPPF as catalysts. The selective formation of the γ-product was attained by the use of Pd(OAc) 2 /DPPE, while the α-product was obtained in the presence of [Pd(π-allyl)(cod)]BF 4 /DPPF. We also succeeded in synthesizing optically active allylic amines using Pd(OAc) 2 /DPPE and [Pd(π-allyl)(cod)]BF 4 /BINAP began from optically active trifluoromethyl-substituted allyl acetate. Furthermore, we established that kinetic resolution of two types of allylic amines was possible using enantioselective isomerization by the [Pd(π-allyl)(cod)]BF 4 /(S)-BINAP catalyst.