Synthesizing graphdiyne with a well-defined structure is a great challenge. We reported herein a rational approach to synthesize graphdiyne nanowalls using a modified Glaser-Hay coupling reaction. Hexaethynylbenzene and copper plate were selected as monomer and substrate, respectively. By adjusting the ratio of added organic alkali along with the amount of monomer, the proper amount of copper ions was dissolved into the solution, thus forming catalytic reaction sites. With a rapid reaction rate of Glaser-Hay coupling, graphdiyne grew vertically at these sites first, and then with more copper ions dissolved, uniform graphdiyne nanowalls formed on the surface of copper substrate. Raman spectra, UV-vis spectra, and HRTEM results confirmed the features of graphdiyne. These graphdiyne nanowalls also exhibited excellent and stable field-emission properties.