Titanium dioxide (TiO2) nanocrystals of different shape were successfully synthesized in a new microemulsion system through a solvothermal process. The TiO2nanocrystals were prepared from the reaction of tetrabutyl titanate (TBT),H2O, and oleic acid (OA), which were used as solvent and surfactant at 300∘Cand 240∘Cin a stainless steel autoclave. The sphere, polygon, and rhombus-shaped nanocrystals have been prepared at 300∘Cand the dot- and- rod shaped nanocrystals have been synthesized at 240∘C. The effect of the reaction time on the shape and size of TiO2nanocrystals in this method was studied in the present paper. The size distribution of TiO2nanocrystals prepared at 300∘Cfor different hours is also studied. In addition, an attempt to describe the mechanism of shape change of TiO2nanocrystals was presented in this paper.