The self-assembly method has been applied for the preparation of structured silicalite-I/ZSM-5 composites. The method has proven to be a controllable and reproducible approach for the preparation of a zoned, thin, oriented coating of silicalite-I on ZSM-5 crystals. b-Orientation of MFI crystals on the ZSM-5 crystals was boosted by pre-coating of the crystals using Ti-butoxide prior to the hydrothermal synthesis of silicalite-I. (c) 2007 Published by Elsevier B.V.