Previous studies performed on samples of MoOF4 dissolved in anhydrous hydrogen fluoride (aHF) solutions have indicated the presence of the [Mo2O2F9]– anion. Building upon this earlier work, MoOF4, and MF (M = Li–Cs) were dissolved in aHF solutions to produce M[Mo2O2F9] (M = Li–Cs) salts. Structural analysis of the obtained compounds was performed using single-crystal X-ray diffraction. This study provides the first single crystal structures for the [MoVI 2O2F9]– anion. Additionally, IR and Raman spectroscopy were used to characterize each salt. These spectra were compared to calculated ones for the solid-state structure of each salt using the DFT-PBE0 density functional method. The calculated spectra were used to give band assignments in the experimentally obtained spectra.