Herein,　we　fabricate　a　multifunctional　molecular　prodrug　BAC　where　the　chemotherapeutical　agent　campto-thecin　(CPT)　is　linked　with　a　boron　dipyrromethene　(BODIPY)-based　photosensitizer　by　an　azobenzene　chain　which　is　sensitive　to　over-expressed　azoreductase　in　hypoxic　tumor　cells.　This　prodrug　was　further　loaded　into　biodegradable　monomethoxy　poly(ethylene　glycol)-b-poly(caprolactone)　(mPEG-b-PCL)　to　improve　its　solubility　and　tumor　accumulation.　The　formed　BAC　nanoparticles　(BAC　NPs)　can　destroy　aerobic　tumor　cells　with　rela-tively　short　distance　from　blood　vessels　by　photodynamic　therapy　(PDT)　under　illumination.　The　PDT　action　inevitably　leads　to　consumption　of　O-2,　and　subsequently　acute　hypoxia　which　can　induce　cleavage　of　azobenzene　linkage　to　boost　release　of　CPT　killing　the　other　hypoxic　interior　tumor　cells　survived　from　PDT.　Both　in　vitro　and　in　vivo　studies　have　verified　that　BAC　NPs　possess　remarkable　antitumor　activity　by　a　synergistic　action　of　PDT　and　chemotherapy.