X-ray diffraction (XRD), transmission electron microscope (TEM), atomic force microscope (AFM), Fourier transform infrared (FTIR) spectra and differential scanning calorimetry (DSC) were used to investigate the structure of KxV2O5.nH2O xerogel films (with 0.0 ≤ x < 0.0091 mol). These films were produced by the sol–gel technique. XRD as well as TEM showed that KxV2O5.nH2O thin films are highly oriented nanocrystals. The particle size as obtained is on the average 12 nm. AFM revealed that the grain shape of the present samples is a rod-like shape. DSC showed an endothermic peak with a minimum ranging between 102 °C and 172 °C due to the intercalation of K+ ions.