Metal–organic frameworks (MOFs), a new class of crystalline molecular solids built from linking organic ligands with metal or metal-cluster connecting points, have recently emerged as a versatile platform for developing single-site solid catalysts. MOFs have been used to drive a range of reactions, including Lewis acid/base catalyzed reactions, redox reactions, asymmetric reactions, and photocatalysis. MOF catalysts are easily separated from the reaction mixtures for reuse, and yet their molecular nature introduces unprecedented chemical diversity and tunability to drive a large scope of catalytic reactions. This Perspective aims to summarize recent progress on light harvesting and photocatalysis with MOFs. The charge-separated excited states of the chromophoric building blocks created upon photon excitation can migrate over long distances to be harvested as redox equivalents at the MOF/liquid interfaces via electron transfer reactions or can directly activate the substrates that have diffused into the MOF channels for photocatalytic reactions. MOF-catalyzed and photodriven proton reduction, CO2 reduction, and organic transformations will be discussed in this Perspective.