The relationship between the nanoscale structure of vanadium pentoxide nanotubes and their ability to accommodate Li+ during intercalation/ deintercalation is explored. The nanotubes are synthesized using two different precursors through a surfactant-assisted templating method, resulting in standalone VOx (vanadium oxide) nanotubes and also "nano-urchin". Under highly reducing conditions, where the interlaminar uptake of primary alkylamines is maximized, standalone nanotubes exhibit near-perfect scrolled layers and long-range structural order even at the molecular level. Under less reducing conditions, the degree of amine uptake is reduced due to a lower density of V4+ sites and less V2O5 is functionalized with adsorbed alkylammonium cations. This is typical of the nano-urchin structure. High-resolution TEM studies revealed the unique observation of nanometer-scale nanocrystals of pristine unreacted V2O5 throughout the length of the nanotubes in the nano-urchin. Electrochemical intercalation studies revealed that the very well ordered xerogel-based nanotubes exhibit similar specific capacities (235 mA h g(-1)) to Na+-exchange nanorolls of VOx (200 mA h g(-1)). By comparison, the theoretical maximum value is reported to be 240 mA h g(-1). The VOTPP-based nanotubes of the nano-urchin 3D assemblies, however, exhibit useful charge capacities exceeding 437 mA h g(-1), which is a considerable advance for VOx based nanomaterials and one of the highest known capacities for Li+ intercalated laminar vanadates.