Abstract Recent studies indicate that the synergistic phototherapy (SPT) process can simultaneously generate heat for photothermal therapy (PTT) and singlet oxygen ( 1 O 2 ) for photodynamic therapy (PDT) to overcome the recurrence of tumors. However, the hypoxic environment in tumors seriously limits the therapeutic effect of the oxygen‐dependent PDT, leading to the domination of PTT in the SPT process. Therefore, it is urgent to develop a novel SPT platform for overcoming hypoxia in tumors and improving the therapeutic effect of both PTT and PDT. In this work, a novel phototherapeutic platform based on a nanocomposite of aza‐BODIPY/manganese dioxide (MnO 2 ) is developed via simple electrostatic self‐assembly. In this design, MnO 2 nanosheets, which could produce heat and catalyze endogenous hydrogen peroxide (H 2 O 2 ) to generate oxygen, are prepared as a nanocarrier. After being coated with the as‐prepared water‐soluble aza‐BODIPY‐based polymer (PPAIB), the obtained MnO 2 @PPAIB performs as a smart phototherapeutic agent for enhancing the efficiency of both PTT and PDT. More importantly, compared to PPAIB, MnO 2 @PPAIB generates more heat and reactive oxygen species to realize the enhanced therapy effects of PTT and PDT. Hence, this work provides a new method to enhance the therapeutic efficacy of SPT by using a polymer/MnO 2 nanoplatform to improve the oxygen concentration and produce more heat.