A sol–gel method (colloidal route) based on V2O5·nH2O hydro-gel was developed to synthesize xK2O-(80-x)V2O5-20MoO3.nH2O (0 ≤ x ≤ 20 mol.%) material. X-ray diffraction (XRD), Transimition electron microscopy (TEM), density, thermoelectric power, and Electrical properties of the as prepared films were investigated. X-ray diffraction, transmission electron micrograph and electron diffraction were used to identify the structure of the obtained nanocrystals. Homogenous nanocrystals of 10.2 nm in size were obtained and were closed packed and are distributed evenly. The density of the samples decreases with increasing K-content. Electrical conductivity and thermoelectric power were measured in the temperature range 300–500 K for the as prepared films. The electrical conductivity showed that all samples were semiconductors and that conductivity increased with increasing K content. The carrier density was evaluated as well. The obtained results showed by increasing K content in the system under investigation, gradual changes in thermoelectric power from n - type to p - type detected. The sol–gel method is fit for the preparation of xK2O-(80-x)V2O5-20MoO3.nH2O material which may offer some favorable properties for commercial application.