Although stannosilicate zeolites are active and selective in Baeyer-Villiger (B-V) oxidation because of their unique Lewis acidity, which is useful to activate the carbonyl group of ketone rather than peroxide, the role of their pore-opening structure and hydrophobicity in selective oxidation still needs to be explored. In the present work, stannosilicate zeolites with different topologies were synthesized and characterized in detail, especially in terms of the coordination states of the Sn species in the isomorphically substituted Sn zeolite Sn-MSE (Sn-MCM-68). The catalytic properties of the synthesized zeolites were evaluated in B-V oxidation. The results show that Sn-MCM-68 possesses some superior catalytic properties in B-V oxidation in comparison with other zeolites, because of its three-dimensional 12 x 10 x 10-membered ring (MR) pore-opening channels and relatively higher hydrophobicity. (c) 2020 Elsevier Inc. All rights reserved.