Nanocrystalline thin film of xNa-(80-x)V2O5-20MoO3.nH2O xerogel obtained by sol gel synthesis. Transimition electron microscopy (TEM), density, electrical properties and thermoelectric power of the as prepared nanocrystalline xNa-(80-x)V2O5-20MoO3.nH2O xerogel thin films (8 ≤ x ≤ 26 mol%) were investigated. These films have been produced by the sol–gel technique (colloidal route). TEM revealed that the samples have nanorods. The particle size was found to be about 10.1 nm. The density of the samples increases with increasing Nacontent. The samples are changes in thermoelectric power from n - type to p - type semiconductors with increasing Na-content. The electrical conductivity shows that all samples are semiconductor and it increases with increasing Nacontent and the activation energy decreases with increasing Na-content. From the best fits, reasonable values of various small polaron hopping parameters were obtained. The electrical conduction at T > θD/2 was due to non-adiabatic SPH.