The cluster Ti3O(OPri)8(benzoate)2 is obtained upon reaction of Ti3O(OPri)10 or Ti3O(OPri)9(OMe) with benzoic acid. The remarkable feature of this substitution reaction is that the cluster structure is approximately preserved. Ti3O(OPri)8(benzoate)2 undergoes a dynamic exchange processes of the propoxy groups in solution.