A polyoxovanadium borate (H2dap)6H［V12B16O54(OH)4］·12H2O(dap=1,2-diaminopropane) with novel structure was hydrothermally synthesized and characterized by the single crystal X-ray diffraction. It crystallizes in triclinic system with space group Pīand unit cell parameters a=19.027(4), b=16.142(3) , c=26.679(5) , α=90°, β=101.06(3) °, γ=90°, V=8042(3) 3, Z=4, Dc=1.962 g·cm－3, μ=1.456 mm－1, F(000)=4 776, the final R1=0.062 6, wR2=0.192 7, S=1. 003, for 7 635 observed reflectionswith I>2σ(I). It is showed that the compound 1 is composed of V12B16 clusters unit and dap which is as a counter ion, and a two-dimensional layered structure is obtained by the effect of hydrogen bonding between the cluster units and dap, and between the layers via strong hydrogen bonds to form a three-dimensional supramolecular structure. The compound 1 were also characterized by IR, two-dimensional infrared (2D IR) correlation spectroscopy with magnetic and thermal perturbation, UV/Vis DRS spectra. The relationship between the structure and spectroscopy properties was discussed. The IR spectrum showed that the antisymmetric stretching vibration absorption peak νas(V—Oμ) and symmetric stretching vibration absorption peaks νs(V—Oμ) appeared at 775 and 683 cm-1 respectively, whereas the vibration absorption peak in ν(B—O) of BO3 and the vibration absorption peak in ν(B—O) of BO4 appeared at 1 350 and 1 050 cm-1 respectively. The response of the stretching vibrations of B—O and V—O was detected in the 2D IR correlation spectra with magentic perturba-tion. In addition, the response of the stretching vibrations of B—OH, B—O and V—O—V was detected in the 2D IR correlation spectra with thermal perturbation.