One‐pot synergistic/cascade reactions represent a promising direction for future catalysis. In particular, the use of solar light to initiate the synergistic/cascade reactions in one pot has attracted increasing attention, with the aim of developing renewable energy–based processes. Metal–organic frameworks (MOFs), are considered to be a promising type of multifunctional catalysts for light‐initiated synergistic/cascade catalysis, due to their excellent photoactive activity and unique structural characteristics, which enable the incorporation of functionally different catalytic active sites to work in concert. Herein, some recent developments on using MOFs as multifunctional catalysts for light‐initiated one‐pot synergistic/cascade reactions are summarized. This review starts with general background information on synergistic/cascade catalysis and the possibility of using MOFs as multifunctional catalysts for light‐initiated synergistic/cascade reactions. Then some examples of designing and fabricating of multifunctional MOFs, including single MOFs, doped MOFs, and metal nanoparticles (MNPs)/MOFs, for a variety of light‐initiated one‐pot synergistic/cascade reactions are demonstrated. Finally, the challenges and the perspective of the development of multifunctional MOFs for light‐induced one‐pot synergistic/cascade reactions are addressed. It is hoped that this review can stimulate future research on the designing and developing of more smart multifunctional MOFs for light‐initiated one‐pot synergistic/cascade reactions.