Highly b-oriented, closely packed, MFI zeolitefilms are prepared on seeded stainless-steel plates using organic template-free,s econdary growth solutions,c ontaining aluminum sulfate as ac rystallization agent. The number of aoriented twin crystals is significantly reduced, and even eliminated, simply by restricting the pH value of the secondary growth solution to the narrowrange of 11.1-11.3. Values of pH can be adjusted through the controlled addition of (NH 4 ) 2 SO 4 or H 2 SO 4 to secondary growth solutions of the composition (1 SiO 2 :0.57 NaOH:137.5 H 2 O:0.0050 (Al 2 (SO 4 ) 3 ·18 H 2 O)) or by simply decreasing the molar composition of NaOH with no extra additives.MFI zeolite films are attractive for aw ide range of applications,i ncluding molecular sieve membranes,c atalytic membrane reactors,l ow-dielectric-constant materials,a nd corrosion-resistant coatings. [1] Both experimental data and simulation results [2] have suggested that the straight channel along the b-axis is the fastest diffusion pathway in MFI crystals and b-oriented zeolite films exhibit superior performance compared to randomly oriented ones. [3] At present, one of the most important applications of b-oriented MFI films is as membranes for separation of p-xylene from xylene isomers. [4] Therefore,s ynthesizing high-quality,b -oriented MFI zeolite films is of great interest from the viewpoint of both fundamental studies and practical applications.B-oriented MFI films have been grown on stainless-steel substrates through the accurate manipulation of synthesis solution composition [5] and kinetic parameters [6] for crystal nucleation and growth during in situ synthesis.Continuous boriented zeolite films and membranes were also successfully prepared on different supports with the secondary (seeded)growth method, taking advantage of ab-oriented zeolite seed layer deposited on the substrate prior to hydrothermal treatment. [7] Decoupling the nucleation and growth steps can significantly reduce the difficulty in manipulating the orientation of zeolite films,w hich in turn enhances the reproducibility and scalability of the zeolite layer synthesis.In the methods mentioned above for the synthesis of boriented MFI zeolite films,o rganic template (or structuredirecting agent, SDA) was necessary for the formation of zeolite crystals.T emplating agents are incorporated in zeolite pores during hydrothermal synthesis and acalcination step is necessary to follow the film/membrane synthesis process to remove the template and open the zeolite channels.D uring the calcination process,a na brupt shrinkage of the zeolite lattice,a nd differences in the thermal expansion characteristics of zeolite films and their supports yield substantial stresses that often result in microcracks in zeolite films. [8] These microcracks make zeolite films less effective in practical applications.Moreover,t he growth of a-oriented twin crystals is unavoidable when tetrapropylammonium hydroxide (TPAOH), the most common template,i su sed in the secondary growth method. [7...