Arynes are highly strained and transient molecules that have been recognized as useful reactive intermediates in synthetic organic chemistry. This chapter illustrates that a wide variety of aryne‐based multicomponent reactions are achievable depending upon electrophilic and transition metal‐catalyzed couplings. It demonstrates the rich chemistry of arynes and their high synthetic significance for constructing diverse aromatic compounds. The remarkable progress in the multicomponent reactions especially in the past decade would be attributable to the use of the Kobayashi's silylaryl triflates as aryne precursors, which allows the generation of arynes at a moderate pace under extremely mild conditions. In view of an increasing demand for the convenient and direct synthesis of complex aromatic compounds found widely in naturally occurring, biologically active, and functional molecules, development of new multicomponent reactions with arynes continues to be of importance in synthetic organic chemistry.