This review begins by the principles that describe the intercalation properties of vanadium pentoxide. Recent developments in the chemical synthesis of vanadium pentoxide nanostructures including nanorod and nanotube arrays, nanowires, anhydrous and hydrous nanorolls and nanobelts, nanoribbons, nanocables and gels are examined. The objective of this review is to demonstrate the use of these nanostructures as cathodes for lithium batteries and electrochromics with high storage capacity and rate performance due to the large surface area and short distance for charge transport compared to the thin film cathodes.