Copper nanoparticles have been found to be catalysts for both homogeneous (stabilized by oligoethyleneglycols) and heterogeneous (immobilized on SiO2) hydroxylation of phenol by hydrogen peroxide to dihydroxybenzenes. The catalysts were synthesized in oligoethyleneglycols by the reduction of coppersalts (supported or nonsupported) using hydrazine. For non-immobilized Cu-nanoparticles high selectivities on dihydroxybenzenes were reached at the conversion of phenol 32% for 30 min at 40 degrees C. It has been demonstrated that adding oxyethylated surfactants to non-immobilized nanoparticles during reaction increased selectivity for the ortho-product. Immobilized Cu-nanoparticles allowed to achieve the conversion of 69% for 15 min at 70 degrees C with selectivity on dihydroxybenzenes more than 95%. (c) 2010 Elsevier B.V. All rights reserved.