Copper(II) triflate was used as a simple and commercially available catalyst in the direct amination of allylic alcohols with anilines to provide C-allylanilines. A wide range of functional groups were tolerated under the reaction conditions, and the products were obtained regioselectivity without the need of an activator. A detailed mechanistic investigation was undertaken. The efficacy of this protocol was demonstrated in the conversion of the 2-allylanilines into substituted quinolines through an oxidative cycloaddition reaction.