Biofilm-related infections, such as dental plaque, chronic sinusitis, native valve endocarditis, and chronic airway infections in cystic fibrosis have brought serious suffering to patients and financial burden to society. Materials that can eliminate mature biofilms without developing drug resistance are promising tools to treat biofilm-related infections, and thus they are in urgent demand. Herein, we designed and readily prepared organic nanoparticles (NPs) with highly efficient photothermal conversion by harvesting energy via excited-state intramolecular motions and enlarging molar absorptivity. The photothermal NPs can sufficiently eliminate mature bacterial biofilms upon low-power near-infrared laser irradiation. NPs hold great promise for the rapid eradication of bacterial biofilms by photothermal therapy.