<p>The development of C-H functionalization methods for directly converting C-H bonds into C-C bonds has drawn significant attention. These reactions typically require the concurrent involvement of distinct catalytic processes, such as photoredox and transition metal catalysis. Combining the corresponding catalytic sites within a single catalyst, instead of adding extra cocatalysts, remains a significant challenge. Here, we present a novel pyridone-based hydrogen-bonded organic framework (HOF), named PFC-943, which exhibits exceptional visible-light absorption properties while integrating both photosensitizing and redox-active sites within its skeleton. Femtosecond transient absorption spectroscopy (fs-TA) reveals that the excited-state electrons of PFC-943 in ethanol exhibit an extended lifetime. Leveraging this unique excited-state electron behavior, PFC-943 converts oxygen into highly reactive singlet oxygen (¹O₂) via an energy transfer (EnT) pathway and facilitates a key carbanion intermediate through a single electron transfer (SET) process. Consequently, the metal-free PFC-943 exhibits remarkable photocatalytic performance in C-H bond arylation reaction of quinoxalin-2(1<i>H</i>)-one. This work presents the first dual-functional HOF for radical-mediated C-H functionalization reactions, offering a novel approach to C-H bond functionalization.</p>