Porous metallic materials are widely used for lithium-ion battery (LIB) electrodes because of their low density, efficient ionic/electron pathways, and high specific surface area. In this study, we fabricate nanoporous Cu using chemical and electrochemical dealloying methods based on a Cu-Ga alloy. The effects of the dealloying conditions on the derived microstructure of the nanoporous metal and its evolution mechanisms are discussed. Analysis and control of the electrochemical dealloying process reveal that the sample morphology can be adjusted and the phase component can be controlled. Accordingly, a 3D CuGa2 electrode with a nanoporous structure is controllably synthesized, and it exhibits a higher specific capacity and cyclic stability than a 2D CuGa2 electrode when used as a LIB anode.