Li2TiO3 compound is one of the most important tritium breeding ceramics for industrial application in the nuclear fusion reactor. The use of the hydrothermal method for preparing ceramic composite materials is new trend. In this work, hybrid nanocomposite microspheres of the nanocrystallites Li2TiO3 were prepared at low temperature 400°C. Nanocomposite powders synthesized by the batch supercritical hydrothermal method for 12 hours under pressure 12MPa. The raw materials were used containing tetrabutyl titanate (Ti(C4H9O)4) as a titanium source, lithium nitrate (LiNO3) as a lithium source, citric acid as a chelating agent and nitric acid as pH controller. The samples were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and X-ray diffraction (XRD). The SEM micrographs showed the synthesized powders have microsphere shape with range size 1 to 3.5 micrometers. XRD result illustrates the microspheres are nanostructure with cubic and monoclinic crystal structures. According to XRD results and using known Scherrer’s equation, the crystallite size of monoclinic phase about 18 nm and monoclinic about 14 nm were determined. The TEM results show that two type of particles morphologies are present in the synthesized microspheres. The first is a spherical shape with a particle size smaller than 100 nm and second is an irregular shape with a particle size between 100 to 200 nm.