Carbon-based hollow nanostructures offer promising potential for a variety of energy-related fields, owing to their special structural characteristics and fascinating physicochemical properties. In this paper, graphdiyne hollow nano spheres (GDY-HNSs) were reported to be prepared through a facile solvothermal synthesis technique with copper oxide nanospheres as both template and source of catalyst. The surface morphologies and the shell thickness of the prepared GDY-HNSs can be easily controlled by simply adjusting the amount of the precursor. Besides, the GDY-HNSs exhibit hierarchical nanostructures, large specific surface areas, and appropriate hollow interior, which offer substantial active sites and contact area between electrode and electrolyte while applied as anode, reducing the diffusion paths for both relative ions and electrons. Thus, while applied in lithium-ion batteries, GDY-HNSs show enhanced electrochemical properties, including higher reversible specific capacity, improved rate capacity and cycling performance compared with most of other carbon materials, even in a large mass loading of 2.0 mg cm⁻².