Photonic functional materials with designable and tunable energy transfer (EnT) processes have become increasingly popular as they significantly broaden the landscape of currently available luminescent materials. Metal–organic frameworks (MOFs), which are constructed from organic ligands and metal ions/clusters, possess highly ordered networks and tunable luminescent properties that make them excellent platforms for exploring EnT mechanisms and designing directional EnT processes. Although the EnT processes in MOFs have been extensively studied, the intricacies of the mechanisms between multiple emitting centers are still relatively unexplored. Thus, the rational design of tunable luminescent materials is quite arduous without a comprehensive understanding of these underlying mechanisms. In this review, the basic theories behind MOFs is systematically introduced from the perspective of the inherent EnT processes. The use of MOFs as ideal platforms for studying EnT processes and developing an efficient engineering strategy for enhancing luminescence and facilitating novel optical behaviors is highlighted. In addition, applications utilizing EnT in MOFs are emphasized, and the future prospects for the development of this technology are discussed.