The gold(I)‐catalyzed retro‐Buchner (decarbenation, retrocyclopropanation) reaction of 7‐substituted cycloheptatrienes has emerged as a safe and powerful alternative for the generation of gold(I) carbenes. These carbenes can cyclopropanate alkenes, take part in intramolecular reactions, or engage in higher cycloadditions with different partners, giving rise to a wide range of relevant structures. This review covers the developments made on the generation of gold(I) carbenes via decarbenation reactions, and the applications of these reactions in organic synthesis.