There is an increasing demand for improvement of the capacity, rate performance, and life cycle of lithium-ion batteries to meet the requirements of low-emission vehicles, such as hybrid electric and plug-in hybrid electric vehicles. In this article, we report the application of graphdiyne (GDY) as high efficiency lithium storage materials and elucidate the method of lithium storage in multilayer GDY. GDY is a novel carbon allotrope comprising sp- and sp2-hybridized carbon atoms. Lithium-ion batteries featuring GDY-based electrode exhibit excellent electrochemical performance, including high specific capacities, outstanding rate performances, and a long cycle lives. We obtained reversible capacities of up to 520mAh/g after 400 cycles at a current density of 500mA/g. At an even higher current density of 2A/g, cells incorporating GDY-based electrodes retained a high specific capacity of 420mAh/g after 1000 cycles.