A water/ethylene glycol (H2O/EG) system has been designed to synthesize lithium niobate (LiNbO3) powders by a mild, one-step quasireverse emulsion method. A morphology transformation from initial nuclei to flowerlike structures and then to hollow spheres is confirmed by the time-dependent experiment. The as-obtained LiNbO3 hollow spheres are formed via Ostwald ripening under solvothermal conditions, and their absorption edge in UV/vis diffuse reflectance spectra can be effectively tuned by the current morphology control strategies. This facile, efficient, and economic work provides a new route to simply and mildly synthesize hollow LiNbO3 particles and is a good initiation in the morphology control study of LiNbO3 powders.