When attempting to use heterocyclic amines containing naphthalene rings, quinoline rings, indole rings, etc. as reaction reagents, only moderate yields can be obtained. In summary, we have demonstrated an efficient, facile and practical one-pot procedure for the synthesis of polysubstituted pyrroles catalyzed by a binuclear copper complexe using EMCCs as precursors for generating 2-aminoallyl cations. A wide variety of poly-substituted pyrroles were obtained in acceptable to good yields under quite mild conditions. This transformation featured a C1,N-dipolar cyclization for 2-aminoallyl cations. We believe that this efficient reaction protocol is attractive for the preparation of a diverse range of tetrasubstituted pyrroles.