The formation mechanisms of garnet-like Li7La3Zr2O12 (LLZO) phase using LiOH?H2O as raw materials are investigated symmetrically by XRD and DTA/TG measurements. It was found that reaction mechanisms of the LLZO formation are as follows: 7Li2O 3La2O3 4ZrO2=2Li7La3Zr2O12 The production of LLZO phase takes place at about 680oC observed from the XRD patterns, in agreement with the thermic peak at 700oC in DTA/TG curves, which arises from the formation of LZZO phase. The stable existence temperature range of LLZO phase is wide, from 720 to 1000oC. However, LLZO is thermally unstable at the high temperatures (>1000oC) due to a serious loss of lithium element, and it discomposes into pyrochlore phase La2Zr2O7. And the amount of the decomposed products increased, and LLZO decreased gradually with the increase of the calcination temperature. When the reactant mixture was calcined at the low temperature, the produced phases were identified to be lanthanum compounds because La2O3 absorbs moisture and CO2 very easily. The chemical reactions at lower temperature are mainly related with the reactions among lanthanum compounds. LLZO powder was synthesized by solid state reaction at 800℃. It is found that the LLZO crystal belongs to the tetragonal symmetry. SEM observations show that the obtained LLZO powder was nano-sized.