Among the Li-ion conducting inorganic materials, lithium lanthanum zirconate (LLZO) is believed to possess good chemical stability against Li metal and hence considered to be a promising solid electrolyte for Li-ion batteries. However, systematic sets of studies conducted here at regular intervals during storage of Al-doped LLZO (cubic garnet) sintered pellets in ambient atmosphere have raised serious concerns over their structural/ mechanical stability/integrity upon exposure to air. Spontaneous cracking/disintegration/pulverization of LLZO pellets takes place after about three weeks of exposure, primarily due to formation of La2Zr2O2 in the LLZO bulk; as found to be thermodynamically feasible at room temperature upon reaction with CO2/moisture. Steep increase in ZrLa2Zr2O2 content coincides with the spontaneous cracking/disintegration. Estimation suggests that internal stresses associated with the formation of La2Zr2O2 from LLZO can be high enough to cause spontaneous fracture. This mandates the development/fabrication/usage of solid-state cells using LLZO under stringent controls against exposure to atmospheric species.