A new Cu-catalyzed asymmetric [3 + 3] cycloaddition of propargyl esters with cyclic enamines is reported. With a combination of Cu(OAc)(2)center dot H2O and a chiral tridentate ferrocenyl-P,N,N ligand as the catalyst, perfect endo selectivities (endo/exo > 98/2) and excellent enantioselectivities (up to 98% ee) for endo cycloadducts were achieved under mild conditions. This method provides a simple and efficient approach for the synthesis of optically active bicyclo[n.3.1] frameworks.