Fluorescence imaging in the second near-infrared window (NIR-II, 1000-1700 nm) holds great promise for in vivo imaging and imaging-guided phototherapy with deep penetration and high spatiotemporal resolution. It is very appealing to obtain NIR-II fluorescent probes through simple procedures and economical substrates. Herein, we developed a D-A-D' structure NIR-II photosensitizer (triphenylamine modified aza-Bodipy, TAB) based on the strong electron-withdrawing nature of borane difluoride azadipyrromethene's center (aza-BODIPY). Subsequently, halogen atoms (Br, I) were introduced to the TAB molecule, and TAB-2Br and TAB-2I were synthesized. Compared to the TAB molecule, a significant redshift in the emission wavelength, ultra-large Stokes shift (>300 nm), and enhanced singlet oxygen production capacity were acquired for the halogenated molecules. After self-assembly of TABs and an amphiphilic polypeptide POEGMA23-PAsp20, the obtained P-TAB, P-TAB-2Br, and P-TAB-2I nanoparticles exhibited excellent water solubility and biocompatibility, remarkable photothermal conversion efficiency (beyond 40%), and good resistance to photobleaching, heat, and H2O2. Under 808 nm laser irradiation, the P-TAB-2I exhibited an efficient photothermal effect and ROS generation in vitro. And in vivo experiments revealed that P-TAB-2I displayed efficient NIR-II fluorescence imaging and remarkable tumor ablation results. All of these results make TAB-2I potential organic probes for clinical NIR-II fluorescence imaging and cancer phototherapy.