Single crystals of a new bismuth vanadate, Bi-3.33(VO4)(2)O-2 was prepared by hydrothermal reaction using a hydrated sodium bismuthate, NaBiO3 center dot nH(2)O as one of the starting compounds. The crystal structure was determined by using single crystal X-ray diffraction data. This compound crystallizes in the triclinic space group P (1) over bar (#2) with a = 7.114(1), b = 7.844(2), c = 9.372(2) angstrom, alpha = 106.090(7), beta = 94.468(7) and gamma = 112.506(8)degrees, Z = 2 and the final R factors are R1 = 0.052 and wR2 = 0.14 for 2085 unique reflections. The crystal structure is composed by four bismuth atoms with the coordination number of 6 or 8 and two VO4 tetrahedra, and one of four bismuth atoms is statistically distributed in the splitting sites with the distance of 0.83 angstrom. This compound exhibited photocatalytic behavior for decomposition of phenol under visible light irradiation and its activity was less than that of monoclinic BiVO4. (C) 2011 Elsevier Ltd. All rights reserved.