We report here, for the first time, the application of ordered, three-dimensional, mesoporous titanosilicates, Ti-SBA-12 and Ti-SBA-16, as reusable solid catalysts, for hydroxylation of phenol, an industrially important organic transformation. The reactions were conducted using 30% aqueous H2O2 as oxidant. The catalysts of this work are more efficient than the hitherto known mesoporous Ti-silicates. They are more para-product selective than TS-1 and other titanosilicates. Ti-SBA-12 exhibited higher activity and hydroquinone/catechol selectivity (by nearly two times) than Ti-SBA-16. H2O2 efficiency of similar to 90 mol% was obtained. Our study reveals that framework substituted Ti with pseudo-tetrahedral geometry, three-dimensional mesoporosity as well as surface structure are the unique features responsible for the high catalytic activity and selectivity of these titanosilicate catalysts. (C) 2012 Elsevier B.V. All rights reserved.