The hydroxylation of a series of oxygenated aromatic compounds (phenols and ethers) with hydrogen peroxide, catalyzed by titanium silicalite TS-1 and a new catalyst TS-1B, was investigated operating in a biphasic reaction medium. In several cases, the reaction afforded phenols with fairly good selectivity. TS-1B is often a better catalyst than the conventional TS-1, displaying higher selectivity on hydrogen peroxide and also higher shape selectivity. So it appears to have some potential in the direct synthesis of selected phenols, in alternative to the conventional multi-step methods. (c) 2007 Elsevier B.V. All rights reserved.