Advances in Donor–Acceptor Covalent Organic Frameworks: From Rational Design to Multifunctional Applications

ABSTRACT Donor–acceptor (D‐A) covalent organic frameworks (COFs) provide modular crystalline platforms in which D‐A pairing, linkage chemistry, pore environments, and framework ordering can be rationally engineered to regulate light harvesting, exciton dissociation, charge separation, and charge transport. This review summarizes recent progress in the design and multifunctional applications of D‐A COFs across key linkage families, including imine, β‐ketoenamine, triazine, vinylene, boroxine, amide, ester, and hydrazone frameworks. We first discuss key structural design principles, including donor/acceptor selection, topology and linkage engineering, π‐π stacking, framework planarity, pore functionalization, and post‐synthetic modification, and relate these features to optoelectronic descriptors such as absorption/emission behavior, energy‐level alignment, and charge‐transfer dynamics. Representative applications are then organized across solar‐driven catalysis, including hydrogen evolution reaction, oxygen evolution reaction, CO 2 reduction, coupled CO–H 2 O 2 generation, as well as sensing/biosensing, biomedical phototherapies, and broadband photodetection. Selected case studies illustrate how specific donor‐acceptor combinations, conjugated linkages, metal centers, and pore microenvironments translate into enhanced performances through structure‐function correlations. Finally, we discuss remaining challenges in operational stability, scalable synthesis, structural precision, and target selectivity, and highlight emerging opportunities in data‐guided design, hybrid integration, and application‐oriented optimization of D‐A COFs for energy, environmental, and biomedical technologies.