Abstract Insufficient T‐cell infiltration seriously hinders the efficacy of tumor immunotherapy. Induction of immunogenic cell death (ICD) is a potentially feasible approach to increase T‐cell infiltration. Since ionizing radiation can only induce low‐level ICD, this study constructs Cu‐based nanoscale coordination polymers (Cu‐NCPs) with mixed‐valence (Cu + /Cu 2+ ), which can simultaneously and independently induce the generation of Cu + ‐triggered hydroxyl radicals and Cu 2+ ‐triggered GSH elimination, to synergize with radiation therapy for potent ICD induction. Markedly, this synergetic therapy remarkably enhances dendritic cell maturation and promotes antitumor CD8 + T‐cell infiltration, thereby potentiating the development of checkpoint blockade immunotherapies against primary and metastatic tumors.