A new glass-ceramic nanocomposites material was prepared by a thermal nanocrystallization of V2O5-Bi2O3-P2O5 system with different V2O5 content. The amorphous state of glassy materials is confirmed by X-ray diffraction. It was shown by XRD and SEM studies that by suitable heat-treatment glasses can be turned into glass-ceramic nanocomposites consisting of crystallites smaller than 80 nm inserted in the glassy matrix. Also, it was shown that thermal nanocrystallization of as-prepared glassy samples leads to creation of nanocrystalline grains of V2O5, Bi2O3, and BiVO4 phases. The glass-ceramic nanocomposites obtained show giant enhancement of electrical conductivity than the as-prepared glasses. The conductivity enhancement was recognized to interfacial regions adjacent crystalline grains. The conduction of the present glasses and their glass-ceramic nanocomposites was confirmed to be due to primarily non-adiabatic hopping of small polaron between vanadium ions.