Copper could be catalyst on the alkenylation reactions of amides, amines, azoles and sulfides, which afforded efficient methods for the synthesis of alkenylamides, enamines, alkenylazoles and alkenylsulfides. Under the conditions of the coupling processes, it would be possible to effect a related transformation as a means to access heterocycles in one-pot. Accordingly, copper-catalyzed double alkenylations of amides, amines and sulfides to afford pyrroles and thiophenes have been expatiated. Furthermore, copper-catalyzed tandem alkenylations of azoles to afford nitrogen-bridgehead azolopyridine derivatives via an N-H bond and its adjacent C-H bond activation have been illustrated.