This article explores the effects of surface area and pore volume on the electrochemical behavior of high surface area V2O5 gels dried by either supercritical or ambient methods. Traditional composite electrode structures have prevented truly quantitative analysis of surface area effects in nanoscale battery materials, as well as a study of their innate electrochemical behavior. These limitations can be overcome by using the "sticky-carbon" electrode technique, which provides a direct electroanalysis of the active material without the use of a composite electrode structure. The resulting electrochemical measurements show pseudocapacitive behavior (1000-2000 F/g) that has not previously been seen for V2O5 aerogels. The relationship between capacitance and pore accessibility is investigated.