Despite the broad reactivity spectrum of diphosphine-based copper(I) photocatalysts, their application often requires high catalyst loadings (10 -20 mol%) due to low photostability. For instance, 2,2′bis(diphenylphosphino)-1,1′-binaphthyl (BINAP)-ligated copper(I) iodide, a widely utilized copper photocatalyst, readily forms a stable iodide-bridged dimer in both solution and solid states, thus making the evaluation of the photocatalytic activity of the monomeric copper species in radical-mediated reactions, complicated. In 2023, He and co-workers designed an innovative strategy to tackle the challenge. They embedded the copper(I)-BINAP photosensitizer within a zinc-based pillar-layered metal-organic framework (MOF15), achieving catalyst immobilization and surface isolation (Figure ). This approach remarkably enhanced turnover numbers, enabling significantly lower catalyst loadings (0.125-0.5 mol%). This MOF-based photocatalyst facilitated various intra-and intermolecular radical-mediated reactions of N-acyloxyimidates and O-acyl oximes. Upon blue light irradiation, the photo-excited catalyst 25.10 underwent oxidative quenching, forming a nitrogen-centered radical This review illustrates the structural, photophysical, and electrochemical properties of homo, and heteroleptic Cu(I)-based photocatalysts, emphasizing the significant achievements of Cu(I)-BINAP complexes for catalyzing challenging chemical reactions. The ability of Cu(I)-BINAP complexes to interact with radicals via innersphere coordination, underscores their promising role to facilitate previously inaccessible synthetic transformations. Furthermore, the efficient incorporation of Cu-BINAP in MOFs, thereby entering the interdisciplinary realm, bridges the gap between material science and organic copper catalysis. While the incorporation of these complexes in asymmetric synthesis remains a sought-after objective, the ability of copper to form heteroleptic complexes with BINAP and a wide range of available chiral ligands as well as merging copper into photo-enzymatic catalysis holds promise for advancing the field in this direction. However, identifying complex mechanistic scenarios in these reactions remains challenging with only available experimental approaches because of the short lifetime of important reactive intermediates, competing side routes for the evolution of excited-state species, and difficulties in determining the kinetic parameters of individual steps. Computational methods are therefore required to fully unravel these mechanisms.