Ion-exchanged NaY zeolite with various valent cations are tested for hydroxylation of benzene and phenol with H2O2 in 1:1 and 3:1 molar ratios, respectively; the highest conversion of benzene (33%) in green one-step process is achieved using Cu-NaY with 100% selectivity to phenol, while OV-NaY shows > 36% phenol conversion with 91% selectivity to catechol, whereas TOF exceeds 1000 with Zn-NaY after 6 h reaction time which is among the highest value reported so far. (C) 2009 Elsevier B.V. All rights reserved.