Regulating Electron Distribution in Regioisomeric Covalent Organic Frameworks for Efficient Solar‐Driven Hydrogen Peroxide Production

Abstract Covalent organic frameworks (COFs) are emerging as a transformative platform for photocatalytic hydrogen peroxide (H 2 O 2 ) production due to their highly ordered structures, intrinsic porosity, and molecular tunability. Despite their potential, the inefficient utilization of photogenerated charge carriers in COFs significantly restrains their photocatalytic efficiency. This study presents two regioisomeric COFs, α ‐TT‐TDAN COF and β ‐TT‐TDAN COF, both incorporating thieno[3,2‐b]thiophene moieties, to investigate the influence of regioisomerism on the excited electron distribution and its impact on photocatalytic performance. The β ‐TT‐TDAN COF demonstrates a remarkable solar‐to‐chemical conversion efficiency of 1.35%, outperforming its α ‐isomeric counterpart, which is merely 0.44%. Comprehensive spectroscopic and computational investigations reveal the critical role of subtle substitution change in COFs on their electronic properties. This structural adjustment intricately connects molecular structure to charge dynamics, enabling precise regulation of electron distribution, efficient charge separation and transport, and localization of excited electrons at active sites. Moreover, this finely tuned interplay significantly enhances the efficiency of the oxygen reduction reaction. These findings establish a new paradigm in COF design, offering a molecular‐level strategy to advance COFs and reticular materials toward highly efficient solar‐to‐chemical energy conversion.