Bacterial infectious diseases, especially those caused by Gram-positive bacteria, have been seriously threatening human health. Preparation of a multifunctional system bearing both rapid bacterial differentiation and effective antibacterial effects is highly in demand, but remains a severe challenge. Herein, we rationally designed and successfully developed a sequence of aggregation-induced emission luminogens (AIEgens) with orderly enhanced D-A strength. Evaluation of structure-function relationships reveals that AIEgens having intrinsic positive charge and proper ClogP value are able to stain Gram-positive bacteria. Meanwhile, one of the presented AIEgens (TTPy) can generate reactive oxygen species (ROS) in extraordinarily high efficiency under white light irradiation due to the smaller singlet-triplet energy gap. Thanks to the NIR emission, excellent specificity to Gram-positive bacteria, and effective ROS generation efficiency, TTPy has been proved to perform well in selective photodynamic killing of Gram-positive bacteria in vitro, such as S. aureus and S. epidermidis, even in S. aureus-infected rat wounds.