Photoassisted　lithium-ion　batteries　provide　an　effective　solution　to　improve　the　capacity　and　round-trip　efficiency　of　batteries　by　utilizing　solar　energy.　However,　there　is　still　a　big　challenge　to　develop　key　photoelectrochemical　energy　storage　materials　for　simultaneous　light　harvesting　and　energy　storage.　Here,　we　presented　a　redox-active　metal-organic　framework　(MOF)　material　with　Ni2+　and　naphthalenediimide　salicylic　acid　ligand　(NDISA)　as　photoactive　electrodes.　The　designed　Ni-NDISA　material　exhibited　reversible　electrochemical　redox　activity　on　the　naphthalenediimide　unit　and　showed　efficient　photoinduced　metal-ligand　charge　transfer　to　realize　solar-to-electrochemical　energy　conversion　and　storage.　With　the　Ni-NDISA　as　a　bifunctional　cathode,　a　photoassisted　lithium-ion　battery　delivered　an　extra　13.1%　of　round-trip　efficiency　and　improved　specific　capacity　(82.0　mA　h　g-1　under　dark　to　200.0　mA　h　g-1　under　1　sun　illumination).　This　work　presents　an　optional　way　to　design　photoelectrochemical　energy　storage　materials　and　opens　up　opportunities　for　solar　to　electrochemical　energy　storage　devices.　©　2024　American　Chemical　Society.