The traditional TS-1 zeolite is a typical microporous material, the diffusion of bulky molecules in TS-1 is greatly affected.[1] Besides, because of the highly hydrolyzable titanium source, the preparation of TS-1 requires complex synthesis conditions. Moreover, the difference in hydrolysis rate between the silicon source and titanium source tends to increase the difficulty of titanium insertion into the framework, and it is easy to generate extraframework Ti species during the synthesis. We propose a method of synthesizing hierarchical TS-1 from highly hydrolysis-resistant polymers containing titanium and silicon (Fig. 1a). This method completely solves the above problems and can conveniently and stably synthesize high-quality TS-1 free of extraframework Ti species. The TS-1 zeolite synthesized from the polymers exhibits excellent reaction performance in the oxidation of n-hexane and cyclohexene.