An efficient and eco-friendly oxidative bromination reaction of phenol has been achieved by treatment with KBr-H2O2 in the presence of a catalytic amount ammonium salt of molybdophosphoric acid or phosphotungstic acid that supported on silica, which were synthesized by sol-gel method. The physicochemical characterization indicated that supported catalysts still retained its Keggin type and the particles were well dispersed onto the surface of silica support. The evaluated results of liquid phase bromination of phenol showed that these catalysts exhibited high catalytic oxybromination activity and high para substituted selectivity, and good stability was also observed after recycling three times. Meanwhile, no highly toxic and corrosive materials were used and formed in the reaction process, which makes this process environmentally benign. The influences of the reaction time, catalyst amount and solvent on oxidative bromination reaction were also investigated. (c) 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.