<p>Vanadium-catalyzed alkene epoxidation has emerged as a versatile and robust approach for the synthesis of epoxides, which are indispensable intermediates in organic synthesis, pharmaceutical development, and natural product chemistry. This review article surveys key advances in epoxidation methodologies employing vanadium-based catalysts, with particular emphasis on widely used systems such as vanadyl acetylacetonate and vanadium oxytriisopropoxide. Attention is given to the use of environmentally benign oxidants, notably hydrogen peroxide and <i>tert</i>-butyl hydroperoxide, as well as to alternative reaction media including ionic liquids and supercritical carbon dioxide. Mechanistic features governing reactivity, selectivity, and asymmetric induction are discussed alongside recent developments in ligand design and catalyst robustness. Collectively, these studies highlight the synthetic utility of vanadium catalysis while underscoring ongoing efforts to enhance selectivity, broaden substrate scope, and improve sustainability.</p> Graphical Abstract <p></p>