Solid electrolytes for solid-state Li-ion batteries are stimulating considerable interest for next-generation energy storage applications. The LLi7La3Zr2O12 garnet-type solid electrolyte has received appreciable attention as a result of its high ionic conductivity. However, several challenges for the successful application of solid-state devices based on Li7La3Zr2O12 remain, such as dendrite formation and maintaining physical contact at interfaces over many Li intercalation/extraction cycles. Here, we apply first-principles density functional theory to provide insights into the Li7La3Zr2O12 particle morphology under various physical and chemical conditions. Our findings indicate Li segregation at the surfaces, suggesting Li-rich grain boundaries at typical synthesis and sintering conditions. On the basis of our results, we propose practical strategies to curb Li segregation at the Li7La3Zr2O12 interfaces. This approach can be extended to other Li-ion conductors for the design of practical energy storage devices.