The plethora of transformations attainable by the transition-metal-catalyzed reactions of arynes has found immense contemporary interest in the scientific community. This review highlights the scope and importance of transition-metal-catalyzed aryne reactions in the field of synthetic organic chemistry reported to date. It covers transformations achieved by the combination of arynes and various transition metals, which provide a facile access to a biaryl motif, fused polycyclic aromatic compounds, different novel carbocycles, various heterocycles, and complex natural products. 1 Introduction 2 Insertion of Arynes 3 Annulation of Arynes 4 Cycloaddition of Arynes 5 Multicomponent Reactions of Arynes 6 Miscellaneous Reactions of Arynes 7 Total Synthesis of Natural Products Using Arynes 8 Conclusion