Anionic compound, bis[1-methyl-3-(3'-sulfopropyl)imidazolium] hexafluorotitanate (1), was proved to be the efficient and recyclable catalyst for the oxidative halogenations of arenes in water using H2O2 as the oxidant and halide salts as the halogenation sources. The mono-halogenated products were obtained selectively by this method. The synergetic catalytic effect coming from the two incorporated functionalities of-SO3H and [TiF6](2-) was manifested in 1. The halogenation rate catalyzed by 1 was in the ranking of NaBr >> NaCl > KI. The UV-vis and FT-IR analyses indicated that the successful formation and regeneration of the active peroxo-Ti species (1A) with the aid of proton acid guaranteed the recycling uses of 1. (C) 2013 Elsevier B.V. All rights reserved.