Despite significant efforts to eliminate bacterial biofilm within root canals, achieving effective disinfection remains challenging due to the complex anatomy and limitations of disinfectants. In this study, a second near-infrared (NIR-II) semiconducting polymer with aggregation-induced emission (AIE) properties, named PIDT-TBT, is deliberately designed and synthesized. This proposes an AIE luminogen-based sterilization strategy in synergy with a low concentration of sodium hypochlorite (NaClO). Water-dispersible PIDT-TBT nanoparticles (NPs) are prepared, demonstrating good biocompatibility, as well as photothermal and photodynamic properties. Subsequent antibacterial tests show that PIDT-TBT NPs exhibit excellent bactericidal effects against three bacterial strains: Staphylococcus aureus, Streptococcus mutans, and Enterococcus faecalis, upon 808nm laser irradiation. In synergy with a low concentration of NaClO (0.5%) solution, PIDT-TBT NPs significantly improves the outcome of root canal treatment under 808nm laser irradiation in a human extracted tooth root canal infection model. Additionally, it is found that PIDT-TBT NPs combine with a low concentration of NaClO solution could safely dissolve dentin debris and further increase the efficiency of root canal preparation by altering the elemental composition of the inner root canal wall.