A new and highly efficient Cu(I)/TF-BiphamPhos catalytic system exhibited excellent reactivity, enantio-/diastereoselectivity, and structural scope in asymmetric 1,3-dipolarcycloaddition of azomethineylides with 0.1-3 mol % of catalyst loading. The present methodology is the best result for asymmetric cycloaddition of azomethineylides, especially derived from amino esters other than glycinate in