The first synthesis of pentoxide vanadium (V2O5) as gel completed 135 years in 2020. Since its first synthesis, the V2O5 has attracted attention over the years in different areas in science and technology. There are several possibilities to obtain V2O5 resulting in different structures. Among these methods, it is possible to mention the sol–gel, hydrothermal/solvothermal synthesis, electrospinning, chemical vapor deposition (CVD), physical vapor deposition (PVD), template-based methods, reverse micelle techniques, Pechini method and electrochemical deposition that can be considered as the great asset for its varied structures and properties. Progress towards obtaining of different structures of V2O5, and phases have been resulted in lamellar structure with wide interlayer spacing, good chemical and thermal stability and thermoelectric and electrochromic properties. Throughout this advancement, its performance for industrial applications have made a strong candidate in electrochromic devices, photovoltaic cell, reversible cathode materials for Li batteries, supercapacitor, among others. This chapter will be to assist an updated review since the first synthesis up to current development.