A novel polyoxovanadium borate Mn2［V12B16O52(OH)6］(en)2(H3O)6(H2O)5 1(en=ethylenediamine) was hydrothermally synthesized and characterized by IR, two-dimensional infrared (2D IR) correlation spectroscopy with magnetic and thermal perturbation, and single crystal X-ray diffraction. In 1， it is interesting that each ［V12B16O52(OH)6］14－ units is connected by four ［Mn(H2O)2］2+ to generate a 2D layer on the ab plane. Along c axis， these layers are further linked by H-bond to form a 3D framework. The response of the stretching vibrations of B—O, V—O—V and Mn—O—B was detected in the 2D IR correlation spectra with magnetic perturbation. In addition, the response of the stretching vibrations of B—OH, B—O, V—O—V and Mn—O—B was detected in the 2D IR correlation spectra with thermal perturbation.