The development of new hierarchical materials capable of efficient energy transfer along a predesigned pathway will boost various applications, ranging from organic photovoltaics to catalytic systems. Due to their exceptional tunability and structural diversity, metal–organic frameworks (MOFs) offer a unique platform to study and model directional energy-transfer processes and, thereby, an efficient path for energy utilization. This article summarizes the latest advances in MOF applications in the fields of optoelectronics, photoswitching, sensing, and photocatalysis, for which development is highly dependent on fundamental studies of MOF photophysics.