The poly crystal multiphase creamics material Li2Mo2-xWxO6 with high conductivity is prepared in reducing atomsphere. By X-ray diffraction, EDX graph, 1R and ESR spectra, it is determined that the sample material is composed of two phases, i.e., Li2Mo1-xWxO4 and MoO2. The addition of tungsten mainly replaces molybdenum in the Li2MoO4 lattice. The electrical properties are studied by a.c. admi tance bridge method and a.c. complex impedance spectroscopy. The conductivity of the sample (x = 0.3) is σ27℃ =1.42×10-2(Ωcm)-1, σ300℃=2.86×10-2(Ωcm)-1. The conductivity increases and the ionic conduction activation energy decreases with increasing tungsten content. The microstructure model and the ionic conduction mechanism are given in this paper.