As an important heterogeneous catalyst, Titanium Silicalite-1 (TS-1) zeolite has been widely applied in various catalytic processes. Here, hierarchical TS-1 single-crystals were successfully synthesized by a steam-assisted crystallization strategy using hierarchically porous titanium-containing silica (Ti-NKM5) as a precursor. Due to the presence of large mesopores (10-40 nm), the microporous structure directing agents penetrated the interstitial structure of silica particles, inducing the dissolution and crystallization process. During crystallization, the generated nanocrystals grew together to form a hierarchical structure. Titanium was fully incorporated into the zeolite framework, and no extra-framework anatase was formed. Compared with the traditional microporous TS-1 zeolite, the synthesized hierarchical TS-1 single-crystal exhibited superior catalytic performance in oxidative desulfurization (ODS) of dibenzothiophene (DBT) and 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT) owing to the hierarchically porous and anatase-free structure. The recycling test revealed the durability of the obtained hierarchical TS-1 catalyst under moderate reaction conditions.(c) 2022 Elsevier Inc. All rights reserved.