Single-crystal X-ray diffraction studies carried out at a synchrotron radiation source have allowed the structure solution and location of fluoride ions inside as-made pure silica zeolites with the IFR and STF framework structures. The local environment of the fluoride has been identified, and unusual ordering of the fluoride ions has been discovered in both cases. The details of the crystal structures are used to suggest structural features that are important in determining the ordering of fluoride ions in zeolites. A mechanism for how the fluoride ordering occurs is suggested for IFR and STF based on the local structure of small cages that make up these zeolites, and the implications for the mechanism of crystal growth are discussed.