A Bi(OTf)(3)/Cu(CH3CN)(4)PF6 system efficiently promoted intermolecular 1:1 hydroamination of 1,3-dienes with various carbamates, sulfonamides, and carboxamides to afford allylic amines in good yield (up to 96%). Reaction proceeded with 0.5-10 mol % catalyst loading at 25-100 degrees C (generally at 50 degrees C) in 1,4-dioxane within 24 h. The Bi(OTf)(3)/Cu(CH3CN)(4)PF6 system constitutes a new entry into series of intermolecular hydroamination catalysis. Mechanistic studies and the postulated reaction mechanism are also discussed.