Lithium (Li) is a key resource driving the rapid growth of the electric vehicle industry globally, with demand and prices continually on the rise. To address the limited reserves of major lithium sources such as rock and brine, research is underway on seawater Li extraction using electrodialysis and Li-ion selective membranes. Lithium lanthanum titanate (LLTO), an oxide solid electrolyte for all-solid-state batteries, is a promising Li-ion selective membrane. An important factor in enhancing its performance is employing the powder synthesis process. In this study, the LLTO powder is prepared using two synthesis methods: sol-gel reaction (SGR) and solid-state reaction (SSR). Additionally, the powder size and uniformity are compared, which are indices related to membrane performance. X-ray diffraction and scanning electron microscopy are employed for determining characterization, with crystallite size analysis through the full width at half maximum parameter for the powders prepared using the two synthetic methods. The findings reveal that the powder SGR-synthesized powder exhibits smaller and more uniform characteristics (0.68 times smaller crystal size) than its SSR counterpart. This discovery lays the groundwork for optimizing the powder manufacturing process of LLTO membranes, making them more suitable for various applications, including manufacturing high-performance membranes or mass production of membranes.