The previously unknown titanium(IV)-containing mu-hydroxo dimeric heteropolytungstate (Bu4N)(7)[(PTiW11O39)(2)-OH] (TBA salt of H1) has been synthesized, starting from H5PTiW11O40, and characterized by elemental analysis, multinuclear (P-31, O-17, W-183) NMR, IR, FAB-MS, cyclic voltammetry, and potentiometric titration. P-31 NMR reveals that H1 (delta -12.76) readily forms in MeCN from the Keggin monomer (POM), PTiW11O405- (2, delta - 13.34), upon the addition of 1.5 equiv of H+, via the protonated species, P(TiOH)W11O394- (H-2, delta -13.44). The ratio of H1, 2, and H2, which are present in equilibrium in MeCN solution at 25 degrees C, depends on the concentration of both H+ and H2O. The Ti-O-Ti linkage readily reacts with nucleophilic reagents, such as H2O and ROH, to yield monomeric Keggin derivatives. mu-Hydroxo dimer H1 shows higher catalytic activity than 2 for thioether oxidation by hydrogen peroxide in acetonitrile. The reaction proceeds readily at room temperature and affords the corresponding sulfoxide and sulfone in ca. quantitative yield. The addition of H2O2 to H1 or H2 results in the formation of a peroxo complex, most likely the hydroperoxo complex P(TiOOH)W11O394-(I), which has P-31 NMR resonance at -12.43 ppm. The rate of the formation of I is higher from Ht than from Ht. When Ht. is used as a catalyst precursor, the rates of the thioether oxidation and peroxo complex formation increase with increasing H2O concentration, which favors the cleavage of H1 to H2. H2O2 in MeCN slowly converts 2 to another peroxotitanium complex, P(TiO2)W11O395- (II), which has P-31 NhlR resonance at - 12.98 ppm. Peroxo complexes I and II differ in their protonation state and interconvert fast on the P-31 NMR time scale. Addition of 1 equiv of H1 completely converts II to I, while 1 equiv of OH- completely converts I to II. P-31 NMR confirms that I is stable under turnover conditions (thioether, H2O2, MeCN). Contrary to two-phase systems such as dichloroethane/aqueous H2O2, no products resulting from the destruction of the Keggin POM were detected in MeCN in the presence of H2O2 (a 500-fold molar excess). The reactivity of I, generated in situ from II by adding 1 equiv of H1, toward organic sulfides under stoichiometric conditions was confirmed using both P-31 NMR and UV-vis spectroscopy. This is a rare demonstration of the direct stoichiometric oxidation of an organic substrate by a titanium peroxo complex.