Furocoumarins represent a relevant family of heterocyclic compounds of natural origin with a wide range of biological activities. Furocoumarins are currently of great interest for medical applications, and research into these compounds is becoming increasingly intense. Although some methods of synthesis of furocoumarins have been known for a long time, in the last few years there have been considerable efforts to develop new approaches for effective preparations of this type of compound. Metal-catalyzed transformations are providing appealing methodologies to access furocoumarin scaffolds in an efficient and atom-economical manner. In this present chapter, metal-catalyzed and metal-mediated routes for the construction of both furan and pyrone rings of furocoumarins are discussed. Synthetic approaches to structurally related coumestan derivatives are also presented.