Novel Li2O-La2O3-ZrO2-P2O5 glass ceramics were successfully prepared by a mechanical ball-milling method and followed by a heat-treatment process. Composition of the glass ceramic electrolytes and the heat-treatment process were optimized by physical characterization and electrochemical measurements. The results show that, the main crystal phases of all the obtained glass ceramics are LiZr2(PO4)(3), and the secondary crystal phases are LaPO4. Both the P2O5 content and sintering temperatures have little effect on the composition of the crystal phases, but have a great influence on the microstructure. Electrochemical impedance spectroscopy (EIS) shows that the P2O5 content has a greater influence on the ionic conductivity of the glass ceramics than the sintering temperature. With the increase of P2O5 content, the activation energy of lithium-ion conduction decreases first and then increases in the range of 0.40-0.49 eV. The sintering temperature has a great influence on the chemical stability and has little effect on the electrical conductivity of glass ceramics. In particular, the 30.3Li(2)O-8.7La(2)O(3)-26.0ZrO(2)-35.0P(2)O(5) glass ceramic exhibits good chemical stability upon exposure to aqueous solutions.