Interlayer expansion of layered zeolite precursors is achieved via the insertion of an additional Tatom in between the layers, typically by means of a silylating agent as source of the T-atom. (3mercaptopropyl)methyldimethoxysilane was used as Si-source in the interlayer expansion of the layered zeolite precursors RUB-36 and RUB-39. The structure expansion was confirmed with PXRD. The incorporation of the silylating agent was followed with 29 Si MAS NMR, 13 C CP MAS NMR and thermogravimetric analysis. The incorporated thiol groups were oxidized with H2O2 to obtain sulphonic acid groups in between the layers. 13 C CP MAS NMR was used to characterize the organic species and monitor the conversion of thiol to propylsulphonic groups. The shapeselective properties of the obtained materials were investigated in acid-catalyzed tetrahydropyranylation reactions.