The article reviews the gold(I)-catalyzed activation of alkynes for the construction of molecular complexity. It covers the general reactivity of alkyne-gold(I) complexes, the addition of heteronucleophiles to alkynes, gold(I)-catalyzed reactions of alkenes with alkynes, and the hydroarylation and hydroheteroarylation of alkynes. The review also discusses oxidative reactions and concludes with a discussion on the scope and organization of the review. The text highlights the versatility of gold(I) complexes in forming carbon–carbon or carbon–heteroatom bonds and their applications in total synthesis.The article reviews the gold(I)-catalyzed activation of alkynes for the construction of molecular complexity. It covers the general reactivity of alkyne-gold(I) complexes, the addition of heteronucleophiles to alkynes, gold(I)-catalyzed reactions of alkenes with alkynes, and the hydroarylation and hydroheteroarylation of alkynes. The review also discusses oxidative reactions and concludes with a discussion on the scope and organization of the review. The text highlights the versatility of gold(I) complexes in forming carbon–carbon or carbon–heteroatom bonds and their applications in total synthesis.