Ultrafine tetragonal BaTiO3 nanocrystals have been prepared by a sol–gel based method. By adjusting the volume ratio of H2O/DEG (diethylene glycol) in the solutions, hydrolysis rate of tetra-n-butyl titanate was strongly inhibited and the particle size could be controlled as small as 4–8 nm. The powder X-ray diffraction and transmission electron microscopy characterizations exhibit that the nanocrystals are spherical and well crystallized. The Raman spectrum shows the products are composed of the orthorhombic phase and tetragonal phase. The Fourier transform infrared spectrum revealed that a surface modification layer was formed around the BaTiO3 nanocrystals, which can prevent them from aggregation and help to form a stable, high solid content sol.