Herein, we first reported that the slow ligand exchange kinetics also occurs in dilute F --bearing aqueous solutions under normal conditions. It is found that such solutions with identical component, but prepared by different pathways with biased initial states, can long-termly exist spectrographic distinguishable different thermodynamic steady states. This makes the solution exhibit an unusual "apparent" structural hysteresis and indicates the significance of solution preparation ways on the thermodynamic studies in solution chemistry domain of sparingly soluble salts.