The transport properties of the glassy Li2O-B2O3-Bi2O3 system, prepared in three different series-I, -II and -III characterized by X-ray powder diffraction, IR, DSC and SEM analyses have been investigated for their ionic and electronic nature using complex impedance and Wagner’s d.c. polarization techniques respectively. Glasses of series-I and -II are found to be ionic, whereas those of series-III, are partially electronic. Electronic contribution increases with the increased concentration of bismuth at the cost of boron. The occurrence of two overlapping semicircles in the complex impedance plane in the case of the samples of series-III has been discussed in the light of two relaxation times due to the presence of Li-B and Li-Bi glassy phases.