Herein, the copper-catalyzed annulation of enaminones with alkynyl esters for the facile synthesis of different pyrroles with a 2,3,4,5-tetrasubstituted structure has been developed. With Cu(OAc)2 as the only catalyst, the tunable synthesis of 2-vinyl and 2,3-dicarboxyl-functionalized pyrroles has been achieved by using terminal and internal alkynyl esters, respectively. The synthesis of 2-vinyl pyrroles represents the first example accessing 2-vinyl substituted pyrroles via direct cascade reactions involving vinylation and pyrrole ring formation.