Due　to　the　aggregation-caused　quenching　effect　and　near-infrared　I　poor　penetration　capabilities　of　common　fluorescent　molecules,　their　applications　in　visualized　imaging　and　photoactivated　treatment　are　limited.　Therefore,　new　near-infrared　II　(NIR-II)　molecule　(named　TST),　which　had　the　abilities　of　aggregation-induced　emission　(AIE)　and　photothermal　therapy　are　synthesized.　Moreover,　in　order　to　further　improve　its　fluorescent　yield　and　therapeutic　effect,　camptothecin　prodrug　(CPT-S-PEG)　and　novel　immune　checkpoint　inhibitor　AZD4635　are　used　to　co-assemble　with　TST　into　nanoparticles　for　drug　delivery.　On　account　of　the　strong　interaction　of　camptothecin　and　TST,　the　intramolecular　rotation　of　TST　is　limited,　thereby　inhibiting　non-radiation　attenuation　and　promoting　fluorescence　generation　when　the　nanoparticles　are　intact.　As　nanoparticles　uptake　by　cancer　cells,　redox　sensitive　CPT-S-PEG　is　degraded　and　the　nanoparticles　disintegrate.　The　released　TST　enhances　non-radiative　attenuation　and　expedites　photothermal　conversion　because　of　the　removal　of　the　constraint　of　camptothecin.　Furthermore,　photothermal　therapy　induces　immunogenic　cell　death　of　cancer　cells　and　releases　abundant　ATP　into　the　tumor　microenvironment　to　recruit　immune　cells.　However,　superfluous　ATP　is　converted　into　immunosuppressive　adenosine　through　the　CD39-CD73-A2AR　pathway.　The　AZD4635　released　by　photothermal　disintegration　of　the　nanoparticles　just　blocks　this　pathway　timely,　achieving　favorable　synergistic　effect　of　photothermal　therapy,　chemotherapy,　and　immunotherapy.　©　2022　The　Authors.　Advanced　Science　published　by　Wiley-VCH　GmbH