Customized Covalent Organic Frameworks with in‐Plane and Intramolecular Asymmetric Polarization for Superior Hydrogen Peroxide Photosynthesis and Aerobic Oxidation of Alcohol

Abstract The design of covalent organic frameworks (COFs) with tailored electronic structures is crucial for enhancing photocatalytic performances and offers an alternative pathway for hydrogen peroxide (H ₂ O ₂ ) synthesis. In this study, the construction of customized COFs featuring in‐plane and intramolecular asymmetric polarization is reported to boost charge separation and redox reactivity. By integrating electron donor and electron acceptor units in the COF skeleton with precise spatial arrangement, an in‐plane and intramolecular polarized electronic environment is achieved that facilitates directional charge transport. The optimized COF with asymmetric electronic distribution exhibits outstanding activity for H ₂ O ₂ photosynthesis under visible light, achieving a high yield of 4524 µmol g ⁻¹ h ⁻¹ in pure water and air without sacrificial agents, demonstrating high productivity and excellent stability. The photocatalytic efficiency further increases to 7316 µmol g ⁻¹ h ⁻¹ at pH 3, demonstrating excellent pH‐responsive behavior. Beyond H ₂ O ₂ synthesis, the optimized COF simultaneously catalyzes value‐added alcohol oxidation reactions, showcasing its multifunctional catalytic capabilities. This work establishes asymmetric polarization engineering as a powerful design principle for COF photocatalysts, providing both fundamental insights into charge separation mechanisms and practical guidelines for developing sustainable photocatalytic systems. The exceptional performance of BT‐COF highlights the vast potential of structurally engineered COFs for solar‐driven chemical transformations.