Metal–Organic Framework‐Based Materials for Dielectric Energy Storage

ABSTRACT Metal–organic frameworks (MOFs) present a unique class of crystalline materials with programmable architectures that enable precise control over dielectric behavior. Their well‐defined metal nodes, organic linkers, and porous structures facilitate polarization mechanisms, critical for high‐performance dielectrics. The beauties of the architectural design strategies from homogeneous MOFs, phase‐engineered heterogeneous MOFs, MOFs incorporated into polymer matrices as fillers for low dielectric loss, stimuli‐responsive MOFs, and conductive MOFs are systematically analyzed to reveal the fundamental interplay between framework structure, charge dynamics, and dielectric functionality. Importantly, their intrinsic structural regularity and defect control support high breakdown strength through deep trap states and uniform electric field distribution. Last but not least, the prospects of MOFs such as device‐level integration, hybridization with 2D materials, and machine learning to connect structure‐polarizability relationships and address their key state‐of‐the‐art challenges are discussed.