In this article, the titanium‐oxo cluster containing bromine had been prepared by solvothermal synthesis, which was used to initiate the atom transfer radical polymerization of butyl methacrylate in order to obtain organic–inorganic hybrid materials. The structures and compositions of titanium‐oxo cluster and its hybrid materials were characterized by X‐ray photoelectron spectroscopy (XPS), 1H nuclear magnetic and infrared spectra tests. The hybrid materials with different molecular weights were dissolved in tetrahydrofuran and coated on the surface of polyethylene terephthalate (PET) film, which was used to study the surface properties. Compared with 89.7% light transmittance of the pure PET film, the light transmittance of the modified films was up to 93.3%. Meanwhile, the water contact angles of the modified films also significantly increased. It would be conducive to the self‐cleaning of the film surface. The coatings prepared by the static respiration diagram method had better hydrophobic effect and show the performance of light scattering. All of that could be proved through the scanning electron microscope (SEM) images. The elastic modulus and hardness of hybrid materials also change with the increase of molecular weight. In addition, the Tg of the hybrid materials increased, which means they have better thermal stability than that of Polybutylmethacrylate (PBMA).