Multifunctional　two-dimensional　(2D)　covalent　organic　polymers　(COPs)　benefiting　from　unique　features　display　great　potential　in　lithium-organic　batteries　yet　are　rarely　reported.　In　this　work,　we　fabricate　a　novel　conjugated　polymer　(TQ-COP)　functioned　with　flexible　crown　ethers　and　pyrazine　redox-active　sites,　used　as　an　organic　rechargeable　battery　cathode.　The　Fourier　transform　infrared　spectroscopy　(FT-IR)　and　13C　cross-polarization　and　magic-angle　spinning　nuclear　magnetic　resonance　(MAS　NMR)　verify　the　chemical　identity　of　redox-active　units　formed　during　polymerization.　In　this　structure,　pyrazine-redox　components　exhibit　a　maximum　six-electron　transfer　per　active　site,　resulting　in　an　initial　specific　capacity　of　162　mA　h/g(20　mA/g).　Because　of　macrocyclic　cavities　and　preferential　coordination　with　the　alkali　metal　ions　of　crown　ethers,　the　rate　determining　step　is　changed　into　a　charge　transfer　process,　urging　TQ-COP　to　emerge　with　a　superior　rate　performance　(132　mA　h/g　at　2　C,　81%　vs.　0.1　C).　Furthermore,　the　introduction　of　crown　ethers　facilitates　photo-excited　charge-carriers　transfer　by　narrowing　the　HOMO-LUMO　gap,　rendering　a　photo-assisted　lithium-organic　battery　with　significant　photovoltage　responses　and　∼10%　improvement　of　battery　round-trip　efficiency　under　illumination,　demonstrating　its　promising　capability　of　solar　energy　utilization.　This　work　proposes　new　insights　into　multifunctional　COPs　for　advanced　lithium-organic　batteries.　©　2022　Elsevier　Ltd