An enhancement in the secondary battery safety demands the optimum synthesis of glass-ceramics electrolytes with modified ionic conductivity. To achieve improved ionic conductivity and safer operation of the battery, we synthesized Li2O included zinc-tellurite glass-ceramics based electrolytes of chemical composition (85-x)TeO2·xLi2O·15ZnO, where x =0, 5, 10, 15mol%. Samples were prepared using the melt quenching method at 800°C followed by thermal annealing at 320°C for 3h and characterized. The effects of varying temperature, alternating current (AC) frequency and Li2O concentration on the structure and ionic conductivity of such glass-ceramics were determined. The SEM images of the annealed glass-ceramic electrolytes displayed rough surface with a uniform distribution of nucleated crystal flakes with sizes less than 1μm. X-ray diffraction analysis confirmed the well crystalline nature of achieved electrolytes. Incorporation of Li2O in the electrolytes was found to generate some new crystalline phases including hexagonal Li6(TeO6), monoclinic Zn2Te3O8 and monoclinic Li2Te2O5. The estimated crystallite size of the electrolyte was ranged from ≈40 to 80nm. AC impedance measurement revealed that the variation in the temperatures, Li2O contents, and high AC frequencies have a significant influence on the ionic conductivity of the electrolytes. Furthermore, electrolyte doped with 15mol% of Li2O exhibited the optimum performance with an ionic conductivity ≈2.4×10−7 Scm−1 at the frequency of 54Hz and in the temperature range of 323–473K. This enhancement in the conductivity was attributed to the sizable alteration in the ions vibration and ruptures of covalent bonds in the electrolytes network structures.