Ultrafine BaTiO 3 nanoparticles and their highly stable sols are prepared by a novel and rapid route. In this method, the formation mechanism that lies between the chemical precipitation and the sol–gel process is proposed. The BaTiO 3 nanocrystal sols are synthesized in as fast as 15 min in an air atmosphere. Dynamic light scattering analysis and the observation of the Tyndall effect confirm the existence of crystalline nanoparticles in these sols. After careful separation, nanocrystalline BaTiO 3 powders with an average particle size as small as 2.8 nm are obtained. These particles have perovskite phase structures as determined by X‐ray diffraction and selected‐area electron‐diffraction analysis. Fourier transform infrared spectroscopy ( FT ‐ IR ) and thermal analysis are used to detect the characteristic functional groups of the solvents on the particles to reveal the formation mechanism. Uniform BaTiO 3 nanocrystal films with high dielectric constants, low dielectric losses, and paraelectric behavior are prepared through solvent evaporation of the nanocrystal sols, providing a new low‐temperature route for the fabrication of perovskite thin films.