Here, we have presented a study of the anionic substructure in the exemplar transition-metal oxyfluoride ReO 3 -type TiOF 2 , using a combination of X-ray PDF, 19 F NMR, DFT modelling, and genetic-algorithm structure-prediction. We find that ReO 3 -type TiOF 2 exhibits strong short-range ordering characterised by preferential cis-O 2 F 4 coordination around titanium. This cis-coordination of titanium allows titanium cations to move away from the centre of their coordination octahe-dra to give shorter Ti-O bonds (and longer Ti-F bonds), giving a net increase in total Ti-X bond strength, relative to more symmetric trans-O 2 F 4 titanium coordination. This preferential cis-TiO 2 F 4 coordination also gives rise to correlated anion disorder , where the configuration of oxygen and fluorine ions decorrelates with separation, resulting in long-range anion disorder that is consistent with the average P m 3m structure model previously proposed from X-ray powder diffraction data .