Singlet oxygen (1O2) is a strong oxidant which plays important roles in photodynamic therapy (PDT).The exploitation of photosensitizers with high 1O2 production is crucial to improve PDT efficiency.In this study,a radical labeled quartet photosensitizer Cy-DENT is reported with high singlet oxygen quantum yield (Φ△=32.3%) due to a radical enhanced inter-system crossing (ISC) process.After the introduction of 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) radical,quartet state 4[R,T]of CyDENT could be formed to give an over 20-fold enhancement of singlet oxygen quantum yield compared to Cy-DEN (without TEMPO radical) under irradiation of near infrared (NIR) light.In addition,the 1O2 production is well controlled by varying the electron-donating ability of the terminal substituent group.Cy-DENT possesses good cell permeability and is localized in mitochondria.Under the irradiation of 700 nm light,Cy-DENT can produce high levels of ROS to destroy the mitochondria membrane potential and induce cell apoptosis.Through the encapsulation ofPEG-SS-PCL micelle,Cy-DENT can be effectively delivered to tumors and suppresses the tumor growth after PDT treatment.