The 50Li(2)O-(50 - chi)TiO2-chiV(2)O(5) with chi = 10, 20, 30 and 40 has been prepared by the solid state reaction method. The conductivity analysis shows metal-semiconductor phase transition around 70degreesC due to the presence of the VO2 phase. The annealing of the samples at 450degreesC for 24 h oxidizes the VO2 phase and the semiconductor-metal phase transition vanishes. The model of Rice and Roth has been built up to calculate the mean free path (l), mobility (mu) and diffusion constant (D). The modulus spectrum of the samples shows the non-Debye nature of the samples. The Fourier Transform Infrared (FTIR) spectrum analysis implies the presence of V2O5 phase in the annealed samples.