Abstract: In contrast with the results previously reported, we have found that Silicalite-2 can be prepared when in the presence of certain amount of alkali metal cations (as chlorides)from NH₄OH-TBAOHsystem. Further, our work demonstrated the essential role played by various alkali metal cations during the crystallization of the Silicalite-2 in crystal transformation, the composition per unit cell, the particle size and morphology of the crystallites.