The　Diels-Alder　reaction　is　a　well-known　[4　+　2]　cycloaddition　in　organic　chemistry,　which　is　employed　in　this　article　as　an　efficient　approach　towards　high-performance　organic　electrode　materials　since　it　can　achieve　the　incorporation　of　more　redox　groups　and　extension　of　π　systems　in　one　step.　As　a　proof-of-concept　example,　we　reported　that　a　hexalithium　benzo[ghi]perylene　hexacarboxylate　(Li6-BPHC)　by　the　lateral　extension　of　well-known　organic　anode　material,　tetralithium　perylene　tetracarboxylate　(Li4-PTC),　via　a　facile　Diels-Alder　reaction,　which　has　been　demonstrated　to　not　only　store　nearly　six　electrons　per　molecule　at　a　current　density　of　280　mA　g−1　but　also　possess　a　highly　stable　cycling　performance　over　100　cycles.　©　2017　Elsevier　Ltd