Abstract: The vanadium(Ⅴ) complex, PyH[VO(Bz)₂Py]Py, has been prepared from NaVO₃, H₂Bz and Py. The single crystal belongs to triclinic in space group, P1, with unit cell constants, α=12.400(5)Å, b= 14.042(5)Å, c= 10.441(4)Å, α=91.92(3)°,β= 93.57(3)°, γ=74.41(3)°, V=1874.7(1,2)ų, Z = 2.Least-spuare refinement has led to a final Rvalue of 0.0450.The coordination number of vanadium is equal to 6, and it is constructed as a distored octahedral form by one Natom and five Oatoms. That complex is a cis-isomer.