Herein, we report a new bioprobe with aggregation-induced emission (AIE) characteristics by conjugation of a far-red/near-infrared emissive AIE luminogen and two polymyxinB peptides. Due to the strong binding effect between polymyxin B and the lipopolysaccharide in the cell wall of Gram-negative bacteria, the bioprobe can selectively visualize Gram-negative bacteria and effectively kill them via photodynamic treatment.