The work presented here demonstrates how the detailed local structure of heteroanionic oxyfluorides can be resolved using a combination of experimental and computational methods. By combining X-ray PDF analysis and 19 F NMR spectroscopy with DFT modelling and genetic algorithm structure prediction we have identified a revised structural model for ReO 3 -type TiOF 2 that is consistent between our experimental and computational analyses. We have also identified how the details of local coordination geometry and bonding direct short-range order in this material, through anions adopting local configurations that maximise Ti-(O/F) bond strength. The general strategy presented here is expected to be generally applicable to other anion-disordered oxyfluorides, where similar short-range deviations from the average crystallographic structure obtained from conventional diffraction methods are also likely.