Herein, a series of triarylboron-based fluorescent probes were developed for distinguishing apoptosis from living cells and even necrosis. They also demonstrate high photosensitivity because they can produce detectable reactive oxygen species (ROS) under an ultra-low light power density (1.5 mW/cm2). By changing the peripheral groups to regulate the performance, we identified a multifunctional probe, TAB-6-amyl, which can be used not only for selectively imaging apoptosis but also for the targeted imaging of SKOV-3 cells in vitro and in vivo. It could further specifically induce the apoptosis of SKOV-3 cells under light irradiation. During the study, we also found that TAB-6-amyl can cross the blood-brain barrier (BBB). Therefore, another probe based on this kind of structure, TAB-5-M-1-cRGD, was constructed for the targeted imaging of brain glioma cells and inducing their apoptosis. This study offers some promising tools for apoptosis detection and tumor photodynamic therapy (PDT).