Constructing highly effective sonosensitizers that integrate tumor microenvironment (TME)-adaptive and ultrasound (US)-controllable production of reactive oxygen species (ROS) to amplify tumor immunotherapies is extremely desirable but remains challenging. Here, inspired by the coordination structure and biocatalytic effects of Fe-based peroxidase, a dual-functional artificial peroxidase is synthesized with ferriporphyrin networks (FePorNW-DAP) to serve a TME-adaptive and US-controllable ROS-generator for amplifying tumor immunotherapies in breast cancer via immunogenic cell death. Owing to the structural advantages of the ferriporphyrin-based large d–π-conjugated networks with the monatomic Fe─N4 coordination center, moderate interaction with H2O2, and decreased bandgap, the FePorNW-DAP displays efficient dual-functional ROS production capabilities to combat tumor cells and amplify the tumor immunotherapies, 1) utilize locally produced H2O2 in the TME to catalytically generate potent •OH and other ROS species; simultaneously, 2) external US irradiation can further boost the generation of •OH and 1O2. This work provides not only critical evidence that the proposed dual-functional artificial peroxidases can induce a strong antitumor immune response and immune memory but also offers essential guidance for creating a high-performance and biocompatible strategy to regulate the immunosuppression TME and enhance the antitumor immune responses of breast cancer.