Synthesis of the novel titanoxane compounds, [(TiCl)(TiOH){(Ti)[μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)](2)(μ-O)}(2)(μ-O)] (4) and [{Ti[μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)](μ-O)}(4)] (5) by controlled reaction of the dinuclear titanium oxo complex [{Ti{μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)}Cl](2)(μ-O)] (1) with 2 equiv of LiOH is reported. Complex 4 is innovative and remarkable. It is one of the rare known examples of tetranuclear stable terminal hydroxo titanium complexes, with an open-chained structure, which coincides with the transient metal monohydroxo proposed in the stepwise pathway employed to justify the formation of the hexanuclear complex [{Ti[μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)](μ-O)}(6)] (3) from 1. (1)H DOSY experiments were used to characterize complex 4. In addition, the structures of compound 5 and of precursor 1 were determined by single-crystal X-ray diffraction studies.