This work addresses the origin of the poor electrochemical activity of triclinic LiVOPO 4. Sample characterization using X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and magnetic measurements indicated the formation of a pure triclinic phase of LiVOPO 4. Diffuse reflectance spectra analysis along with a density functional theory (DFT) calculation showed that triclinic LiVOPO 4 is a wide bandgap semiconductor which is confirmed by a very large resistance measured using AC impedance technique. All these experimental characterization and theoretical investigations suggest that the poor electrochemical performance of the triclinic LiVOPO 4 is primarily associated with its extremely low intrinsic electronic conductivity.