MXenes, a two-dimensional (2D) material, exhibit excellent optical, electrical, chemical, mechanical, and electrochemical properties. Titanium-based MXene (Ti-MXene) has been extensively studied and serves as the foundation for 2D MXenes. However, other transition metals possess the potential to offer excellent properties in various applications. This comprehensive review aims to provide an overview of the properties, challenges, key findings, and applications of less-explored vanadium-based MXenes (V-MXenes) and their composites. The current trends in V-MXene and their composites for energy storage and conversion applications have been thoroughly summarized. Overall, this review offers valuable insights, identifies potential opportunities, and provides key suggestions for future advancements in the MXenes and energy storage/conversion applications.