The highly efficient copper-catalyzed homo-dimerization and cross-coupling of propargyl esters have been developed. Various 1-en-3,5-diynes, [5]cumulenes and 1,3-diynes were successfully furnished via the copper-allenylidene intermediates with moderate to excellent yields. Migratory insertion is proposed as the key step to achieve the selectivity at the carbene carbon of the copper-allenylidene.