Glasses of the Li2O-V2O5-P2O5 system of different extent of glass-network disruption, characterized by a parameter r=[Li2O]/[V2O5 + P2O5], were synthesized. They were subsequently characterized by differential scanning calorimetry (DSC), electron paramagnetic resonance (EPR) and impedance spectroscopy. As in the case of glasses of the Ag2O-V2O5-P2O5 system, studied earlier by us, one observes a transition from predominantly electronic to predominantly ionic conduction. EPR spectra of predominantly ionically conducting glasses under study exhibit hyperfine structure (hfs). In the case of electronically conducting glasses, the hyperfine structure of EPR lines is absent.