In (η6‐p‐cymene)(difluorophosphinato‐κO){2‐[(1H‐pyrazol‐1‐yl)methyl‐κN2]pyridine‐κN}ruthenium(II) 0.85‐hexafluorophosphate 0.15‐tetrafluoroborate, [Ru(PO2F2)(C10H14)(C9H9N3)](PF6)0.85(BF4)0.15, (I), the [PO2F2]− ligand exhibits positional disorder due to one F atom and one O atom sharing the same two positions related by a mirror reflection across the O—P—F plane. The correct composition of this coordinated anion was successfully determined to be [PO2F2]− by refining the complex with various tetrahedral anions in which terminal atoms have similar atomic form factors. The noncoordinated counter‐ion is compositionally disordered between [PF6]− and [BF4]−. The difficulty in determining the correct composition of this anion illustrates the importance of a crystallographer remaining impartial and open to encountering unexpected moieties in the process of elucidating a structure.