To summarize, the research team proposed a dual-state activation strategy that simultaneously utilizes both S₁ and T₁ excited states in D–A COFs for efficient photocatalysis. The structurally optimized D–A COFs exhibit broad-spectrum absorption extending into the near-infrared region and high performance with a high TOF under red-light irradiation. Additionally, they operate without metals, co-catalysts, or sacrificial donors while facilitating various condensation and coupling reactions with exceptional efficiency and selectivity. This approach surpasses the traditional limitation of selectively using only one excited state, significantly enhancing photocatalytic efficiency and broadening reaction scope for applications like renewable energy and environmental remediation.