© 2022, The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.In this study, vanadium oxide coated thin films on the p-Si substrate were prepared by the sol–gel method using V2O5 powder as a precursor. The crystal structures, surface morphology, and content of the films were investigated by XRD, SEM, AFM, and EDX analysis, respectively. Metal–oxide–semiconductor (MOS) structures were fabricated on the p-Si wafer and the electrical properties of those were obtained from current–voltage (I-V) and capacitance–voltage (C–V) measurements. As a result of XRD analysis, V8O15 and V3O7 structure peaks were observed in the films. The frequency and voltage-dependent capacitance measurements for MOS structures showed that the capacitance decreased with increasing frequency. The main electrical parameters for instance diode ideality factor (n), barrier height (ΦB), series resistance (RS) of the MOS structure were determined from the current–voltage (I–V) characteristics and compared in detail with thermionic emission theory, Norde and Cheung methods.