<p>Covalent Organic Frameworks (COFs) have emerged as a preeminent class of crystalline porous materials, bridging the gap between molecular precision and heterogeneous photo-electrocatalysis. This review highlights recent breakthroughs in COF-based materials, emphasizing how their unique architectural features including long-range π-conjugation, permanent porosity, and modular tunability to enable superior photon harvesting and accelerated charge carrier dynamics for renewable fuel generations. Specifically, the synthesis methods, fundamental principles, linkage and block bond effects, and applicable design strategies of COFs are reviewed. We also summarize and criticize current literature related to the fundamental mechanisms driving key transformations of COFs in the targeted application such as hydrogen evolution, CO₂ reduction, nitrogen fixation, and H₂O₂ production, as the core study of this review. The strategic refinements in synthesis, architectural properties, and co-catalyst integration that have pushed performance of COFs toward industrial relevance are also discussed. Further challenges and potentials of COFs in energy generation sector are critically suggested. Ultimately, this review provides a critical perspective on the evolving role of COFs in green fuel production, serving as a strategic roadmap for the development of next-generation materials essential to achieving global net-zero emissions and sustainable future.</p> Graphical abstract <p></p>