Using the first-principles calculations, we explored the feasibility of using graphdiyne, a 2D layer of sp and sp2 hybrid carbon networks, as lithium ion battery anodes. We found that the composite of the Li-intercalated multilayer α-graphdiyne was C6Li7.31 and that the calculated voltage was suitable for the anode. The practical specific/volumetric capacities can reach up to 2719 mAh g-1/2032 mAh cm-3, much greater than the values of ∼372 mAh g-1/∼818 mAh cm -3, ∼1117 mAh g-1/∼1589 mAh cm-3, and ∼744 mAh g-1 for graphite, graphynes, and γ-graphdiyne, respectively. Our calculations suggest that multilayer α-graphdiyne can serve as a promising high-capacity lithium ion battery anode.