Light‐mediated therapies such as photodynamic therapy (PDT) is considered as emerging cancer treatment strategies. However, there are still lots of defect with common photosensitizers (PSs), such as short emission wavelength, week photostability, poor cell permeability and low PDT efficiency. Therefore, it is very important to develop high‐performance PSs. Recently, luminogens with aggregation‐induced emission (AIE) characteristics and Red/near‐infrared (NIR) emissive have been reported as promising PSs for image‐guided cancer therapy, due to prevent autofluorescence in physiological environments, their enhanced fluorescence in the aggregated state and generation of reactive oxygen species (ROS). Herein, we developed PSs named TBTCPM and MTBTCPM with donor‐acceptor (D‐A) structures, strong Red/near intra‐red (NIR), excellent targeting specificities to good cell permeability and high photostability. Interestingly, both of them can efficiently generate reactive oxygen species under white light irradiation and possess excellent killing effect on cancer cells. This study, thus, not only demonstrates applications in cell image‐guided PDT cancer therapy performances. but also provide strategy for construction of AIEgens with long emission wavelengths.