A mild and efficient catalyst system for asymmetric Friedel-Crafts alkylation of indoles with trifluoropyruvates was reported. The chiral ligands took the advantages of both the proline and the binaphthyl moieties, and the in situ prepared Cu(II) catalyst showed good substrate tolerance in the reactions. Indoles bearing different substituents could be tolerated, and the desired products could be obtained in up 99 % yields and up to 98 % ee. Especially, the reactions could be carried out in gram scale without the loss of stereoselectivity, and some of products were able to achieve 99 % ee after simple crystallization.