sec-Butanol-modified rounded-coffin-shaped silicalite-1 (SL) microcrystals were assembled into a compact and highly b-oriented monolayer extending over the centimeter scale via the Langmuir-Blodgett (LB) technique. For comparison, methanol- or ethanol-modified SL microcrystals could not float and were compressed into a dense film in an LB trough. Subsequently, highly b-oriented MFI films with a thickness of similar to 1.5 mu m were successfully obtained on the solid substrates by secondary growth of the LB monolayer using tetrapropylammonium hydroxide (TPAOH) as the structure-directing agent. The electrochemical experiments confirmed that the prepared films were defect-free. In general, the LB method is a highly controllable and reproducible method of organizing anisotropic zeolite crystals with a preferred orientation over a relatively large surface area. The LB technique could be further applied as an effective platform for the oriented assembly of different types of zeolite particles and the growth of variously oriented zeolite films.