The composition of the mother liquor in the course of synthesis of silicalite by the fluoride method has been monitored by C-13, F-19 and Si-29 NMR and by atomic absorption spectrometry. The Si content never exceeds 5% of the total Si content. Several distinct fluorosilicate species apart from SiF62- coexist in a complex dynamic equilibrium in the solution. The results indicate that synthesis proceeds via the type B solid-solid transformation mechanism, and we describe the successive reaction steps.