The epoxidation and successive pinacol formation of tri- and tetraalkyl-substituted olefins using Ti-beta/H2O2/H(2)Oas the catalytic system has been investigated. Aluminum-free Ti-beta exhibits better activity and pinacol selectivity than TS-1, TS-2, Ti-MCM-22, and mesoporous Ti-MCM-41. Pinacol (vic-diol) is obtained as the major product with small amounts of the side products pinacolone, alcohol (via hydration), and oligomers. The conversion and pinacol selectivity increase with an increase in reaction temperature and time. The change in product distribution with reaction time over Ti-beta shows that the epoxide is the initial product which undergoes a secondary reaction to give pinacol as the major product. The conversion and H2O2 selectivity decrease with the bulkiness of the substituents at the C=C bond but the selectivity of pinacol is not significantly affected. The reactivity of cyclic 1-methyl-1-cyclohexene is considerably lower than that of the corresponding open-chain analogue 2-methyl-2-butene. The symmetrical tetramethyl-substituted 2,3-dimethyl-2-butene led to the formation of small amount of dimers over medium-pore titanium silicates TS-1, TS-2, and Ti-MCM-22. The epoxidation of these substituted olefins proceeded more rapidly when using acetonitrile as a cosolvent than under triphase conditions. Mechanistically, the primary epoxide product undergoes acid-catalyzed nucleophilic ring opening by H2O molecules to give pinacol.