Cancer recurrence and metastasis are two major challenges in the current clinical therapy. Here, we synthesized a novel diketopyrrolopyrrole-based photothermal reagent (DCN) with unique J-aggregation-induced redshift to achieve efficient tumor thermal ablation under safe power (0.33 W/cm2). Meanwhile, S-nitroso-N-acetylpenicillamine (SNAP) was co-loaded with near-infrared (NIR)-absorbing DCN in amphiphilic polymers to realize heat-induced massive release of nitric oxide (NO), which could form oxidant peroxynitrite (ONOO–) to active MMPs, thereby degrading the compact tumor extracellular matrix (ECM) to improve the ablation depth and infiltration of immune cells. Through a facile supramolecular assembly method, the DCN/SNAP nanoparticles were anchored to liquid nitrogen-frozen cancer cells (LNF), achieving enhanced anti-tumor immune responses and effective inhibition of distant tumor and pulmonary metastases after only one treatment. The safety and effectiveness of this supramolecular cell-conjugation platform were verified by 2D/3D cellular experiments and bilateral tumor model, confirming the thermal ablation-gas permeation-antigen presentation therapeutic mode had promising anticancer prospects.