The glass-forming region of the Li2O-V2O5-P2O5 system was examined. The glass transition temperature and stability of glass were enhanced with increasing P2O5 content. Li2O-V2O5-P2O5 glasses show electronic or ionic conduction depending on the glass composition. The electronic conductivity increases with increasing V2O5 content, while the ionic conductivity is proportional to the Li2O content. The effect of crystallization on the electrical conduction was also investigated. The ionic conductivity decreased by thermal crystallization. Drastic increase of electronic conduction was observed in the crystallization process in glasses of 50Li(2)O-25V(2)O(5)-25P(2)O(5) and its neighboring compositions. It was clarified that high electronic conduction occurs in a metastable crystalline phase prior to the thermal equilibrium crystallization. (C) 2009 Published by Elsevier B.V.