Graphdiyne,as the novel carbon allotrope,which is composed of sp2-and sp-hybridized carbon,has exhibited excellent catalytic activity and conductivity.It has been applied in series of fields,such as Li-battery,catalyst and energy conversion.Expanding well-defined structures and useful applications of graphdiyne is still full of challenges in material chemistry.Herein,we optimized the synthesis condition of pyrenyl-graphdiyne to obtain the nanowall structure.Compared with the typical nanosheet structure,the pyrenyl-graphdiyne nanowalls(Pyr-GDY-NWs)have more area for lithium insertion.Lithium-ion battery featuring Pyr-GDY-NWs-based electrode exhibits a high reversible specific capacity up to 1464 mA·h/g,which is triple than that of the commercial graphite.We also used the theoretical calculation to investigate the mechanism of Li storage in Pyr-GDY-NWs.The experiment and theoretical data showed that Pyr-GDY-NWs had the potential application in lithium batteries.Therefore,Pyr-GDY with a defined structure would be applied in energy storage and energy conversion.