The combination of photoredox and transition metal catalysis, known as metal aphotoredox catalysis, is a powerful platform for building complex molecules under mild conditions. In particular, metal aphotoredox-catalyzed multicomponent coupling reactions require no high-temperature or moisture- and air-sensitive organometallic reagents compared to conventional single-transition metal-catalyzed reactions and enable the rapid production of value-adding chemicals from readily available starting materials. In the last few years, a multitude of metal aphotoredox-catalyzed multicomponent couplings have been developed in order to simultaneously build CC and CX bonds and even build chiral frameworks under mild conditions. These multicomponent reactions can be roughly divided into alkene difunctionalizations, alkyne difunctionalizations, propellane difunctionalizations, etc. on the basis of their different radical receptors. While considerable advances have been made in this area, further efforts are still required to meet the demands of modern green synthetic chemistry. In this Review, we summarize the recent advances in the field of metal aphotoredox-catalyzed multicomponent coupling reactions and provide directions for future development.

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