The synthesis and the characterization of a new octanuclear carboxylated titanium oxo-cluster [Ti8O10(OOCR)(12)] [R = CH(CH3)(2) and CCl3] is reported. The structure was characterized by single-crystal X-ray diffraction. It consists in four vertices-linked pairs of edge-sharing TiO6 octahedra, presenting 2 and 3 oxygen atoms. O-17 and C-13 liquid state NMR was performed with results in full accordance with the structure determined by X-ray diffraction. During synthesis, solvothermal conditions and a large excess of carboxylic acid allow to remove all alkoxo ligands of the titanium alkoxide precursor and lead to stable purely carboxylate clusters. This family of clusters can therefore be considered as interesting SBUs to elaborate new metal-organic frameworks.