The comparison of DFT optimization results and experimental structure data has shown that the PBE-D3 calculations deliver a correct prediction of the lowest-energy fluoride location in the majority of cases. This indicates that calculations at this level of theory, which are relatively routinely feasible with state-of-the-art computing resources, can be used to search for likely fluoride locations, either to validate the experimentally determined positions or to predict them in cases where an unambiguous determination from diffraction data is not possible. The combination of XRD, DFT, and solid-state NMR methods can enable a very comprehensive structural characterization. Previous work on MWW-and AST-type zeolites has shown that the energetic ordering of different configurations is strongly influenced by the presence of the OSDA molecules, which should therefore be included in the calculations. As a consequence, the correct localization of the organic cations in the larger zeolite pores may, in many cases, be the larger challenge. However, if the OSDA cations are correctly placed in the structure model, the present results indicate that there is reason to be confident about the fluoride positions obtained from DFT. As discussed, this issue could be, at least partially, responsible for the discrepancies between calculations and experiment observed for STF, where the initial positions of the DMASD + cations were obtained using force field calculations. Although this is, generally, a well-tested procedure, the orientation of the OSDA might be different in real samples, or several orientations might coexist. It cannot be ruled out that an erroneous OSDA orientation would affect the energetic ordering obtained from DFT.