We then consider the effect of variations in anionic short-range order on the lithium intercalation properties of ReO 3 -type TiOF 2 . By performing additional DFT calculations, we show that the local anion substructure can have a significant effect on lithium intercalation voltages, with an example fully-ordered low-energy structure and the maximally disordered special-quasi-random 4 × 4 × 4 supercell structure showing a difference of mean lithium intercalation voltage of > 1.5 V as well as a large increase in the spread of intercalation voltage values. Because the precise short-range structure of ReO 3 -type TiOF 2 may be affected by different synthesis protocols, this result indicates that it may be possible to tune the electrochemical intercalation behaviour of TiOF 2 -and, by analogy, of other transition-metal heteroanionic materials-through careful design of synthesis routes.