Owing to easy copper efflux, the deficiency of targeting delivery and limited tissue penetration depth of light, the combination therapy of cuproptosis and phototheranostics remains enormous challenges towards triple-negative breast cancer (TNBC). To overcome these obstacles, a NIR-II excitation multifunctional nanomedicine is prepared by self-assembly of targeting aptamers (AS1411) utilizes metallic copper ions as coordination nodes, followed by coated with ultrasmall NIR-II polymer dots (Pdots) with excellent optical performances, forming a carrier-free hybrid nanosystem. After positive targeting into TNBC through specific recognition of aptamer towards cell surface nucleolin, Pdots loaded in nanomedicine enable NIR-IIa fluorescence/NIR-II photoacoustic imaging-guided NIR-II photothermal therapy (PTT) under NIR-II (1064 nm) light excitation, achieving precise phototheranostics of TNBC tumors. The loaded Cu(II) is reduced to cytotoxic Cu(I) by intracellular glutathione (GSH) and ferredoxin 1 (FDX1), synchronously enabling chemodynamic therapy (CDT) and inducing cuproptosis against TNBC. NIR-II PTT and GSH depletion further enhance therapeutic efficiency of CDT and cuprptosis through cell sensitization. This work provides a new attempt to integrate NIR-II phototheranostics and cuproptosis into a single nanoplatform with targeting capability for synergistic therapy of TNBC.