The recent studies indicate that internal point defects in solid electrolytes modify the electronic and ionic conductivity and relaxation mechanism of solid oxide fuel cells. We focused on synthesis of Lithium (Li) doped Zn_1-xCo_xO (x = 0.00, and 0.10) nanoparticles employing chemical synthesis technique with a reflux setup under constant Argon gas flow. The structural characterizations were performed by x-ray powder diffractometer (XRD) and x-ray photoelectron spectroscopy (XPS). Then, Rietveld refinements were performed to investigate the replacement of Li atom amount in ZnO lattice. Moreover, the variations in ionic conduction dependent on 5, 10 and 20 mol% Li doped ZnO were analysed via ac impedance spectroscopy. The complex measurements were performed in an intermediate temperature range from 100 °C to 400 °C. Ac conductivity responses of each sample were disappeared at a certain temperature due to becoming electronic conductive oxides. However, this specific temperature was tuned to high temperature by Li doping amount in ZnO lattice. Furthermore, the activation energy change by Li dopant amount implied the tuneable ionic conduction mechanism.