A method was developed for the synthesis of free-standing silicalite-l membranes. Intergrown polycrystalline films were synthesized at the interface between a colloid-free aqueous phase and an organic phase or air. These films were characterized by scanning electron microscopy (SERI) and X-ray diffraction (XRD). It was found that the crystallites of the films formed at the air-water interface were oriented with their (010) axis orthogonal to the interface.