Pure phase of sillenite structure, Bi12TiO20, was directly synthesized using stoichiometric bismuth (III) nitrate pentahydrate and titanium glycolate by co-precipitation. The influence of pH on the structure of Bi12TiO20 was studied in the pH range of 3-10. The sillenite structure was characterized using XRD and FTIR. The photo-degradation reaction of 4-nitrophenol (4-NP) was used to study photocatalytic activity of Bi12TiO20 as a function of the preparation pH. The rate of decomposition was followed by UV-vis and TOC. The beginning concentration of 4-NP, 44 ppm, decreased to less than 1 ppm within 30 min for all prepared catalysts. It was found that the decomposition rate constant of B12TiO20 is six times higher than those of either TiO2 or Bi2O3 under the same conditions. (c) 2005 Elsevier B.V. All rights reserved.