AbstractFrom the past decade so far, the synthesis of seven‐membered oxacycles especially natural monocyclic oxepines and their annulated derivatives has received considerable attention. Due to the importance of these valuable scaffolds in natural products, pharmaceuticals, and prospective drugs, as well as their strong potential for use in the biosynthesis and metabolism of monocyclic and polycyclic aromatic compounds, a variety of synthesis strategies have been proposed to afford oxepine moiety. Among the versatile and attractive approaches, this review article focuses on the exciting developments in transition metal‐mediated reactions as the key step in the synthesis of oxepine derivatives from 2010 to early 2021.